Water based concentrated product forms of light stabilizers made by a heterophase polymerization technique

ABSTRACT

The instant invention pertains to a concentrated aqueous dispersion of organic light stabilizers with a particle size of less than 1000 nm, prepared by heterophase radical polymerization of ethylenically unsaturated monomers in the presence of the light stabilizers, wherein the weight ratio of light stabilizer to polymeric carrier is greater than 50/100. Another aspect of the invention is a process for the preparation of such aqueous dispersions with high light stabilizer content. Aqueous dispersions prepared according to this process are useful ingredients for adhesives, aqueous emulsions of natural or synthetic rubbers, water based inks or a water based coating compositions, which are consequently also subjects of the invention.

The instant invention pertains to a concentrated aqueous polymerdispersion with a particle size of less than 1000 nm containing organiclight stabilizers, prepared by heterophase radical polymerization ofethylenically unsaturated monomers in the presence of the lightstabilizers, wherein the weight ratio of light stabilizer to polymericcarrier is greater than 50 parts light stabilizer per 100 parts polymercarrier. Another aspect of the invention is a process for thepreparation of such aqueous dispersions with high light stabilizercontent. Aqueous dispersions prepared according to this process areuseful ingredients for adhesives, aqueous emulsions of natural orsynthetic rubbers, water based inks or water based coating compositions,which are consequently also subjects of the invention.

Non-polar light stabilizers like organic UV-absorbers (UVA) orsterically hindered amines (HALS) are well known additives andfrequently used to protect coatings from degradation, especially withrespect to outdoor weathering. Paints or coatings for demandingapplications typically contain up to 5% by weight of organic lightstabilizers, based on total binder solids. But unlike in solvent-basedcoatings, in modern water based coatings, many of the well-establishednon-polar light stabilizers are difficult to incorporate due toinsolubility and/or incompatibility with the aqueous coating or paintformulations. Depending on the type of coating or paint formulation andthe type of light stabilizers, it can be impossible to generate a stableuniform mixture. In other cases it may occur that the initialhomogeneous formulations show instability upon storage leading toseparation of the light stabilizers and/or other components. Therefore,typical undesired phenomena, such as floating, sedimentation, serumformation, gelation, etc may occur. Such phenomena caused by theincompatibility of the light stabilizers are detrimental, for example,for a coatings performance. Accordingly several attempts have been madeto overcome the incompatibility problems mentioned above.

Non-polar light stabilizers, such as UV-absorbers, have been chemicallymodified with polar groups in order to enhance watersolubility/compatibility and to provide the light stabilizers moleculeswith self-emulsifying properties in water. This approach has thedisadvantage that the chemical modification is usually complex, ratherexpensive, and the surfactant-like behavior of polar modified lightstabilizers can cause environmental problems as well as a lowerperformance due to washing out of the light stabilizers under humidconditions and outdoor weathering.

Attempts have also been made to incorporate the light stabilizersalready into the binder polymers at the stage of manufacture of thebinder polymer, in order to achieve a uniform distribution of the lightstabilizers already in the binder raw material. However, this approachis very inflexible, because it requires that the light stabilizers donot interfere with any process stage during the manufacture of thebinder polymer. The target amount of light stabilizer is already fixedwith the binder polymer and no degree of freedom is left to adjust orenhance the light stabilizer level during or after formulation of thepaint. To cover a broader range of coating formulations with differentbinders and various types and/or amounts of light stabilizers, anextended stock of light stabilizer-modified binder resins would benecessary. This is usually very impractical for a paint producer.

Non-polar light stabilizers can be formulated to concentrated stableaqueous emulsions or dispersion by the use of relatively high amounts ofemulsifiers or surfactants, typically with more than 10-20% emulsifieror surfactant relative to active UVA. Such concentrated light stabilizeremulsions or dispersions can be used in different aqueous formulations,but the relative high amount of surfactants can impair water sensitivityor lack of adhesion to the substrate of the final coating.

EP 0 942 037 discloses polymer dispersions containing a polymer phaseinto which a polymer stabilizer is incorporated. Incorporation of thestabilizer is carried out by swelling the final aqueous polymerdispersion with an organic solvent in which the stabilizer has beendissolved. A polymerization step in presence of the light stabilizer isnot involved. The approach is limited to certain lightstabilizer/polymer combinations because not every light stabilizerpenetrates easily into a more or less swollen polymer.

Recently EP 1 191 041 disclosed aqueous polymer dispersions, which havebeen prepared by radical miniemulsion polymerization of an ethylenicallyunsaturated monomer in which a dye, UV-absorber or optical brightener isdissolved. The polymerization is carried out in the presence of anon-ionic, surface active compound and an amphiphilic polymer. Theamount of dye, UV-absorber or optical brightener ranges from 0.5 to 50%by weight based on the weight of the final polymer matrix. The aqueousdispersions are useful as ingredients for cosmetic applications.

As mentioned above, the polymer dispersions disclosed in EP 1 191 041provide the desired additive in a concentration of 0.5 to 50% by weight,based on the polymer matrix. In other words the polymer, which does notcontribute to the desired effect, is present in a by far higher amountthan the additive. Exemplified are less than 20% UV-absorber based onthe monomer weight. Although this may be acceptable for cosmeticformulations, the requirements for coatings, inks and plasticapplications are different.

For instance the concentration of light stabilizer in the polymermatrix, which serves as a carrier, should be as high as possible inorder to add as little as possible of undesired material, which canadversely affect weathering properties, to the coating, ink or plasticcomposition.

It has now been found that concentrated aqueous polymer dispersions witha particle size of less than 1000 nm can be prepared by heterophaseradical polymerization of ethylenically unsaturated monomers in thepresence of light stabilizers, wherein the weight ratio between lightstabilizer and polymer carrier is greater than 50 parts of lightstabilizer to 100 parts of the polymer carrier.

One aspect of the invention is a concentrated aqueous polymer dispersionwith an average particle size of less than 1000 nm comprising

-   -   a) a polymer carrier prepared by heterophase radical        polymerization of at least one ethylenically unsaturated monomer        in the presence of    -   b) a non-polar organic light stabilizer        wherein the weight ratio of non-polar organic light stabilizer        to polymer carrier is greater than 50 parts of light stabilizer        per 100 parts of polymer carrier.

Optionally a non-ionic, cationic or anionic surfactant, preferably anon-ionic or cationic one may be added.

Preferably more than one ethylenically unsaturated monomer is used. Whenthe polymerization is carried out with two or more monomers, at leastone may carry two unsaturated functionalities in order to provide acertain degree of crosslinking. For example the amount of thedifunctional monomer may vary from 0.5 to 20% by weight based on thetotal weight of the monomer mixture.

Preferred is a concentrated aqueous polymer dispersion wherein theweight ratio of non-polar organic light stabilizer to polymer carrier isequal or greater than 80 parts per 100 parts, more preferred greater 100parts per 100 parts and most preferred greater 120 parts per 100 parts.

In a specific embodiment of the invention, the weight ratio of lightstabilizer to polymer carrier is from 120 parts of the light stabilizerper 100 parts of polymer carrier to 200 parts of the light stabilizer to100 parts of polymer carrier.

Preferably the average particle size is less than 500 nm, morepreferably less than 250 nm.

Droplet (oil/water emulsion) as well as particle (polymer dispersion)size can be measured by using dynamic light scattering (DLS) technique(also known as photon correlation spectroscopy (PSC) or quasi-elasticlight scattering (QELS)). For this kind of measurement a NICOMP particlesizer (NICOMP Model 380, Particle Sizing System, Santa Barbara, Calif.,USA) with a fixed scattering angle of 90° can be used for example. Themeasurement leads to the mean diameter D_(INT) (intensity weighted).

The total solids content of the concentrated aqueous polymer dispersionis for example more than 20%, for instance more than 30% and preferablymore than 40% by weight based on the total weight of the aqueousdispersion. In a particularly preferred embodiment the total solidscontent is more than 50% by weight based on the total weight of theaqueous dispersion.

For example the non-polar organic light stabilizer is selected from thegroup consisting of a hydroxyphenyl benzotriazol UV-absorber, ahydroxyphenyl triazine UV-absorber, a hydroxybenzophenone UV-absorber,an oxalic anilide UV-absorber and a sterically hindered amine lightstabilizer or mixtures thereof.

In a preferred embodiment the non-polar organic light stabilizer has awater solubility of less than 1% preferably less than 0.1% and mostpreferably of less than 0.01% by weight at room temperature andatmospheric pressure.

The right balance between solubility in water and solubility in themonomer droplets influences strongly the polymerization result.Therefore the polarity of the non-polar organic light stabilizer canalso be expressed in terms of log p.

The partition coefficient log p (octanol/water) is a widely usedparameter for example in rating the environmental impact of chemicalcompounds. Its calculation is described by W. M. Meylan, P. H. Howard inJ. Pharmaceutical Sciences 84, (1995), 83-92.

In the context of the present invention the non-polar organic lightstabilizer has preferably a log p value of more than log p=2.

For example the ethylenically unsaturated monomer is selected from thegroup consisting of styrene, substituted styrene, conjugated dienes,acrolein, vinyl acetate, vinylpyrrolidone, vinylimidazole, maleicanhydride, (alkyl)acrylic acidanhydrides, (alkyl)acrylic acid salts,(alkyl)acrylic esters, (alkyl)acrylonitriles, (alkyl)acrylamides, vinylhalides or vinylidene halides.

For instance the ethylenically unsaturated monomer is a compound offormula CH₂═C(R_(a))—(C═Z)—R_(b), wherein Z is O or S; R_(a) is hydrogenor C₁-C₄alkyl, R_(b) is NH₂, O⁻(Me⁺), glycidyl, unsubstitutedC₁-C₁₈alkoxy, C₂-C₁₀₀alkoxy interrupted by at least one N and/or O atom,or hydroxy-substituted C₁-C₁₈alkoxy, unsubstituted C₁-C₁₈alkylamino,di(C₁-C₁₈alkyl)amino, hydroxy-substituted C₁-C₁₈alkylamino orhydroxy-substituted di(C₁-C₁₈alkyl)amino, —O—CH₂—CH₂—N(CH₃)₂ or—O—CH₂—CH₂N⁺H(CH₃)₂An⁻;

An⁻ is a anion of a monovalent organic or inorganic acid;

Me is a monovalent metal atom or the ammonium ion.

Examples for specific ethylenically unsaturated monomers are styrene,isobutylmethacrylate, cyclohexylmethacrylate, hydroxyethylmethacrylate,methylmethacrylate, benzylmethacrylate, vinyl toluene, n-butylacrylate,tert-butylacrylate, methylacrylate, ethylacrylate, propylacrylate,hexylacrylate or hydroxyethylacrylate.

A particular suitable monomer mixture is a mixture ofhydroxyethylmethacrylate, methylmethacrylate, cyclohexylmethacrylate,vinyl toluene, methylmethacrylate, isobutylmethacrylate.

Examples of acids from which the anion An⁻ is derived areC₁-C₁₂carboxylic acids, organic sulfonic acids such as CF₃SO₃H orCH₃SO₃H, mineralic acids such as HCl, HBr or HI, oxo acids such as HClO₄or complex acids such as HPF₆ or HBF₄.

Examples for R_(a) as C₂-C₁₀₀alkoxy interrupted by at least one O atomare of formula

wherein R_(c) is C₁-C₂₅alkyl, phenyl or phenyl substituted byC₁-C₁₈alkyl, R_(d) is hydrogen or methyl and v is a number from 1 to 50.These monomers are for example derived from non ionic surfactants byacrylation of the corresponding alkoxylated alcohols or phenols. Therepeating units may be derived from ethylene oxide, propylene oxide ormixtures of both.

Further examples of suitable acrylate or methacrylate monomers are givenbelow.

wherein An⁻ and R_(a) have the meaning as defined above and R_(e) ismethyl or benzyl. An⁻ is preferably Cl⁻, Br⁻ or ⁻O₃S—CH₃.

Further acrylate monomers are

Examples for suitable monomers other than acrylates are

Preferably R_(a) is hydrogen or methyl, R_(b) is NH₂, glycidyl,unsubstituted or with hydroxy substituted C₁-C₄alkoxy, unsubstitutedC₁-C₄alkylamino, di(C₁-C₄alkyl)amino, hydroxy-substitutedC₁-C₄alkylamino or hydroxy-substituted di(C₁-C₄alkyl)amino; and

Z is oxygen.

Acrylic acid esters and methacrylic acid esters are typicallyC₁-C₁₈alkyl esters.

Preferred is a concentrated aqueous polymer dispersion wherein theethylenically unsaturated monomer is selected from the group consistingof C₁-C₁₈acrylates, C₁-C₁₈methacrylates, acrylic acid, (meth)acrylicacid, styrene, vinyltoluene, hydroxy-functional acrylates or(meth)acrylates, acrylates or (meth)acrylates derived from alkoxylatedalcohols and multifunctional acrylates or (meth)acrylates or mixturesthereof.

Particularly useful methacrylates are iso-butylmethacrylate,cyclohexylmethacrylate.

In a specific embodiment the concentrated aqueous polymer dispersion isprepared from a mixture of at least two of the above monomers and atleast one monomer which is bifunctional, so that a crosslinked polymeris obtained. The amount of bifunctional monomer is for example from 0.5to 20 weight-%, based on the weight of the sum of monomers.

Typical examples for bifunctional monomers are divinyl-benzene,ethyleneglycol diacrylate, butyleneglycol diacrylate or diethyleneglycoldiacrylate.

The monomers or monomer mixtures have preferably a low water solubility,which is below 5%, more preferred below 0.5% and most preferred below0.1% by weight.

Preferably in the concentrated aqueous polymer dispersion thehydroxybenzophenone is of formula I

the 2-hydroxyphenylbenzotriazole is of formula IIa, IIb or IIc

the 2-hydroxyphenyltriazine is of formula III

and the oxanilide is of formula (IV)

in the compounds of the formula (I) v is an integer from 1 to 3 and w is1 or 2 and the substituents Z independently of one another are hydrogen,halogen, hydroxyl or alkoxy having 1 to 12 carbon atoms;in the compounds of the formula (IIa),R₁ is hydrogen, alkyl having 1 to 24 carbon atoms, phenylalkyl having 1to 4 carbon atoms in the alkyl moiety, cycloalkyl having 5 to 8 carbonatoms or a radical of the formula

R₄ and R₅ independently of one another are alkyl having in each case 1to 5 carbon atoms, or R₄, together with the radical C_(n)H_(2n+1−m),forms a cycloalkyl radical having 5 to 12 carbon atoms,m is 1 or 2, n is an integer from 2 to 20 andM is a radical of the formula —COOR₆ in whichR₆ is hydrogen, alkyl having 1 to 12 carbon atoms, alkoxyalkyl having ineach case 1 to 20 carbon atoms in the alkyl moiety and in the alkoxymoiety or phenylalkyl having 1 to 4 carbon atoms in the alkyl moiety,R₂ is hydrogen, halogen, alkyl having 1 to 18 carbon atoms, andphenylalkyl having 1 to 4 carbon atoms in the alkyl moiety, andR₃ is hydrogen, chlorine, alkyl or alkoxy having in each case 1 to 4carbon atoms or —COOR₆ in which R₆ is as defined above, at least one ofthe radicals R₁ and R₂ being other than hydrogen;in the compounds of the formula (IIb)T is hydrogen or alkyl having 1 to 6 carbon atoms,T₁ is hydrogen, chlorine or alkyl or alkoxy having in each case 1 to 4carbon atoms,n is 1 or 2 and,if n is 1,T₂ is chlorine or a radical of the formula —OT₃ or

if n is 2, T₂ is a radical of the formula

in whichT₃ is hydrogen, alkyl which has 1 to 18 carbon atoms and isunsubstituted or substituted by 1 to 3 hydroxyl groups or by —OCOT₆,alkyl which has 3 to 18 carbon atoms, is interrupted once or severaltimes by —O— or —NT₆- and is unsubstituted or substituted by hydroxyl or—OCOT₆, cycloalkyl which has 5 to 12 carbon atoms and is unsubstitutedor substituted by hydroxyl and/or alkyl having 1 to 4 carbon atoms,alkenyl which has 2 to 18 carbon atoms and is unsubstituted orsubstituted by hydroxyl, phenylalkyl having 1 to 4 carbon atoms in thealkyl moiety, or a radical of the formula —CH₂CH(OH)-T₇ or

T₄ and T₅ independently of one another are hydrogen, alkyl having 1 to18 carbon atoms, alkyl which has 3 to 18 carbon atoms and is interruptedonce or several times by —O— or —NT₆-, cycloalkyl having 5 to 12 carbonatoms, phenyl, phenyl which is substituted by alkyl having 1 to 4 carbonatoms, alkenyl having 3 to 8 carbon atoms, phenylalkyl having 1 to 4carbon atoms in the alkyl moiety or hydroxyalkyl having 2 to 4 carbonatoms,T₆ is hydrogen, alkyl having 1 to 18 carbon atoms, cycloalkyl having 5to 12 carbon atoms, alkenyl having 3 to 8 carbon atoms, phenyl, phenylwhich is substituted by alkyl having 1 to 4 carbon atoms, phenylalkylhaving 1 to 4 carbon atoms in the alkyl moiety,T₇ is hydrogen, alkyl having 1 to 18 carbon atoms, phenyl which isunsubstituted or substituted by hydroxyl, phenylalkyl having 1 to 4carbon atoms in the alkyl moiety, or —CH₂OT₈,T₈ is alkyl having 1 to 18 carbon atoms, alkenyl having 3 to 8 carbonatoms, cycloalkyl having 5 to 10 carbon atoms, phenyl, phenyl which issubstituted by alkyl having 1 to 4 carbon atoms, or phenylalkyl having 1to 4 carbon atoms in the alkyl moiety,T₉ is alkylene having 2 to 8 carbon atoms, alkenylene having 4 to 8carbon atoms, alkynylene having 4 carbon atoms, cyclohexylene, alkylenewhich has 2 to 8 carbon atoms and is interrupted once or several timesby —O—, or a radical of the formula —CH₂CH(OH)CH₂OT₁₁OCH₂CH(OH)CH₂— or—CH₂—C(CH₂OH)₂—CH₂—,T₁₀ is alkylene which has 2 to 20 carbon atoms and can be interruptedonce or several times by —O—, or cyclohexylene,T₁₁ is alkylene having 2 to 8 carbon atoms, alkylene which has 2 to 18carbon atoms and is interrupted once or several times by —O—,1,3-cyclohexylene, 1,4-cyclohexylene, 1,3-phenylene or 1,4-phenylene, orT₁₀ and T₆, together with the two nitrogen atoms, are a piperazine ring;in the compounds of formula (IIc)R′₂ is C₁-C₁₂alkyl and k is a number from 1 to 4;in the compounds of the formula (III)u is 1 or 2 and r is an integer from 1 to 3, the substituentsY₁ independently of one another are hydrogen, hydroxyl, phenyl orhalogen, halogenomethyl, alkyl having 1 to 12 carbon atoms, alkoxyhaving 1 to 18 carbon atoms, alkoxy having 1 to 18 carbon atoms which issubstituted by a group —COO(C₁-C₁₈alkyl);if u is 1,Y₂ is alkyl having 1 to 18 carbon atoms, phenyl which is unsubstitutedor substituted by hydroxyl, halogen, alkyl or alkoxy having 1 to 18carbon atoms;alkyl which has 1 to 12 carbon atoms and is substituted by —COOH,—COOY₈, —CONH₂, —CONHY₉, —CONY₉Y₁₀, —NH₂, —NHY₉, —NY₉Y₁₀, —NHCOY₁₁, —CNand/or —OCOY₁₁;alkyl which has 4 to 20 carbon atoms, is interrupted by one or moreoxygen atoms and is unsubstituted or substituted by hydroxyl or alkoxyhaving 1 to 12 carbon atoms, alkenyl having 3 to 6 carbon atoms,glycidyl, cyclohexyl which is unsubstituted or substituted by hydroxyl,alkyl having 1 to 4 carbon atoms and/or —OCOY₁₁, phenylalkyl which has 1to 5 carbon atoms in the alkyl moiety and is unsubstituted orsubstituted by hydroxyl, chlorine and/or methyl, —COY₁₂ or —SO₂Y₁₃, or,if u is 2,Y₂ is alkylene having 2 to 16 carbon atoms, alkenylene having 4 to 12carbon atoms, xylylene, alkylene which has 3 to 20 carbon atoms, isinterrupted by one or more —O— atoms and/or is substituted by hydroxyl,—CH₂CH(OH)CH₂—O—Y₁₅—OCH₂CH(OH)CH₂, —CO—Y₁₆—CO—, —CO—NH—Y₁₇—NH—CO— or—(CH₂)_(m)—CO₂—Y₁₈—OCO—(CH₂)_(m), in whichm is 1, 2 or 3,Y₈ is alkyl having 1 to 18 carbon atoms, alkenyl having 3 to 18 carbonatoms, alkyl which has 3 to 20 carbon atoms, is interrupted by one ormore oxygen or sulfur atoms or —NT₆- and/or is substituted by hydroxyl,alkyl which has 1 to 4 carbon atoms and is substituted by —P(O)(OY₁₄)₂,—NY₉Y₁₀ or —OCOY₁₁ and/or hydroxyl, alkenyl having 3 to 18 carbon atoms,glycidyl, or phenylalkyl having 1 to 5 carbon atoms in the alkyl moiety,Y₉ and Y₁₀ independently of one another are alkyl having 1 to 12 carbonatoms, alkoxyalkyl having 3 to 12 carbon atoms, dialkylaminoalkyl having4 to 16 carbon atoms or cyclohexyl having 5 to 12 carbon atoms, or Y₉and Y₁₀ together are alkylene, oxaalkylene or azaalkylene having in eachcase 3 to 9 carbon atoms,Y₁₁ is alkyl having 1 to 18 carbon atoms, alkenyl having 2 to 18 carbonatoms or phenyl,Y₁₂ is alkyl having 1 to 18 carbon atoms, alkenyl having 2 to 18 carbonatoms, phenyl, alkoxy having 1 to 12 carbon atoms, phenoxy, alkylaminohaving 1 to 12 carbon atoms or phenylamino,Y₁₃ is alkyl having 1 to 18 carbon atoms, phenyl or alkylphenyl having 1to 8 carbon atoms in the alkyl radical,Y₁₄ is alkyl having 1 to 12 carbon atoms or phenyl,Y₁₅ is alkylene having 2 to 10 carbon atoms, phenylene or a group-phenylene-M-phenylene- in which M is —O—, —S—, —SO₂—, —CH₂— or—C(CH₃)₂—,Y₁₆ is alkylene, oxaalkylene or thiaalkylene having in each case 2 to 10carbon atoms, phenylene or alkenylene having 2 to 6 carbon atoms,Y₁₇ is alkylene having 2 to 10 carbon atoms, phenylene or alkylphenylenehaving 1 to 11 carbon atoms in the alkyl moiety, andY₁₈ is alkylene having 2 to 10 carbon atoms or alkylene which has 4 to20 carbon atoms and is interrupted once or several times by oxygen;in the compounds of the formula (IV) x is an integer from 1 to 3 and thesubstituents L independently of one another are hydrogen, alkyl, alkoxyor alkylthio having in each case 1 to 22 carbon atoms, phenoxy orphenylthio.

C₁-C₁₈alkyl may be linear or branched. Examples of alkyl having up to 18carbon atoms are methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl,isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl,1,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl,1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl,2-ethylhexyl, 1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl,decyl, undecyl, 1-methylundecyl, dodecyl, 1,1,3,3,5,5-hexamethylhexyl,tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl.

In the compounds of the formula (IIa) R₁ can be hydrogen or alkyl having1 to 24 carbon atoms, such as methyl, ethyl, propyl, butyl, hexyl,octyl, nonyl, dodecyl, tetradecyl, hexadecyl, octadecyl, nonadecyl andeicosyl and also corresponding branched isomers. Furthermore, inaddition to phenylalkyl having 1 to 4 carbon atoms in the alkyl moiety,for example benzyl, R₁ can also be cycloalkyl having 5 to 8 carbonatoms, for example cyclopentyl, cyclohexyl and cyclooctyl, or a radicalof the formula

in which R₄ and R₅ independently of one another are alkyl having in eachcase 1 to 5 carbon atoms, in particular methyl, or R₄, together with theC_(n)H_(2n+1−m) radical, forms a cycloalkyl radical having 5 to 12carbon atoms, for example cyclohexyl, cyclooctyl and cyclodecyl. M is aradical of the formula —COOR₆ in which R₆ is not only hydrogen but alsoalkyl having 1 to 12 carbon atoms or alkoxyalkyl having 1 to 20 carbonatoms in each of the alkyl and alkoxy moieties. Suitable alkyl radicalsR₆ are those enumerated for R. Examples of suitable alkoxyalkyl groupsare —C₂H₄OC₂H₅, —C₂H₄OC₈H₁₇ and —C₄H₈OC₄H₉. As phenylalkyl having 1 to 4carbon atoms, R₆ is, for example, benzyl, cumyl, α-methylbenzyl orphenylbutyl.

In addition to hydrogen and halogen, for example chlorine and bromine,R₂ can also be alkyl having 1 to 18 carbon atoms. Examples of such alkylradicals are indicated in the definitions of R₁. R₂ can also bephenylalkyl having 1 to 4 carbon atoms in the alkyl moiety, for examplebenzyl, a-methylbenzyl and cumyl.

Halogen as a substituent means in all cases fluorine, chlorine, bromineor iodine, preferably chlorine or bromine and more preferably chlorine.

At least one of the radicals R₁ and R₂ must be other than hydrogen.

In addition to hydrogen or chlorine, R₃ is also alkyl or alkoxy havingin each case 1 to 4 carbon atoms, for example methyl, butyl, methoxy andethoxy, and also —COOR₈.

In the compounds of the formula (IIb) T is hydrogen or alkyl having 1 to6 carbon atoms, such as methyl and butyl, T₁ is not only hydrogen orchlorine, but also alkyl or alkoxy having in each case 1 to 4 carbonatoms, for example methyl, methoxy and butoxy, and, if n is 1, T₂ ischlorine or a radical of the formula —OT₃ or —NT₄T₅. T₃ is here hydrogenor alkyl having 1 to 18 carbon atoms (cf. the definition of R₁). Thesealkyl radicals can be substituted by 1 to 3 hydroxyl groups or by aradical —OCOT₆. Furthermore, T₃ can be alkyl having 3 to 18 carbon atoms(cf. the definition of R₁) which is interrupted once or several times by—O— or —NT₆- and is unsubstituted or substituted by hydroxyl or —OCOT₆.Examples of T₃ as cycloalkyl are cyclopentyl, cyclohexyl or cyclooctyl.T₃ can also be alkenyl having 2 to 18 carbon atoms.

Suitable alkenyl radicals are derived from the alkyl radicals enumeratedin the definitions of R₁. These alkenyl radicals can be substituted byhydroxyl. Examples of T₃ as phenylalkyl are benzyl, phenylethyl, cumyl,α-methylbenzyl or benzyl. T₃ can also be a radical of the formula

Like T₃, T₄ and T₅ can, independently of one another, be not onlyhydrogen but also alkyl having 1 to 18 carbon atoms or alkyl which has 3to 18 carbon atoms and is interrupted once or several times by —O— or—NT₆-. T₄ and T₅ can also be cycloalkyl having 5 to 12 carbon atoms, forexample cyclopentyl, cyclohexyl and cyclooctyl. Examples of T₄ and T₅ asalkenyl groups can be found in the illustrations of T₃. Examples of T₄and T₅ as phenylalkyl having 1 to 4 carbon atoms in the alkyl moiety arebenzyl or phenylbutyl. Finally, these substituents can also behydroxyalkyl having 1 to 3 carbon atoms.

If n is 2, T₂ is a divalent radical of the formula

In addition to hydrogen, T₆ (see above also) is alkyl, cycloalkyl,alkenyl, aryl or phenylalkyl; examples of such radicals have alreadybeen given above.

In addition to hydrogen and the phenylalkyl radicals and long-chainalkyl radicals mentioned above, T₇ can be phenyl or hydroxyphenyl andalso —CH₂OT₈ in which T₈ can be one of the alkyl, alkenyl, cycloalkyl,aryl or phenylalkyl radicals enumerated.

The divalent radical T₉ can be alkylene having 2 to 8 carbon atoms, andsuch radicals can also be branched. This also applies to the alkenyleneand alkynylene radicals T₉. As well as cyclohexylene, T₉ can also be aradical of the formula —CH₂CH(OH)CH₂OT₁₁OCH₂CH(OH)CH₂— or—CH₂—C(CH₂OH)₂—CH₂—.

T₁₀ is a divalent radical and, in addition to cyclohexylene, is alsoalkylene which has 2 to 20 carbon atoms and which can be interruptedonce or several times by —O—. Suitable alkylene radicals are derivedfrom the alkyl radicals mentioned in the definitions of R₁.

T₁₁ is also an alkylene radical. It contains 2 to 8 carbon atoms or, ifit is interrupted once or several times by —O—, 4 to 10 carbon atoms.T₁₁ is also 1,3-cyclohexylene, 1,4-cyclohexylene, 1,3-phenylene or1,4-phenylene.

Together with the two nitrogen atoms, T₆ and T₁₀ can also be apiperazine ring.

Examples of alkyl, alkoxy, phenylalkyl, alkylene, alkenylene,alkoxyalkyl and cycloalkyl radicals and also alkylthio, oxaalkylene orazoalkylene radicals in the compounds of the formulae (I), (IIa), (IIb),(IIc), (III) and (IV) can be deduced from the above statements.

Within the benzotriazole UV-absorbers those according to formula IIa arein general preferred.

The UV absorbers of the formulae (I), (IIa), (IIb), (IIc), (III) and(IV) are known per se and are described, together with their preparationin, for example, WO 96/28431, EP-A-323 408, EP-A-57 160, U.S. Pat. No.5,736,597 (EP-A-434 608), U.S. Pat. No. 4,619,956, DE-A 31 35 810 andGB-A 1 336 391. Preferred meanings of substituents and individualcompounds can be deduced from the documents mentioned.

In another embodiment the UV-absorbers of the class of hydroxyphenyltriazines are of formula (IIIa)

in which n is 1 or 2;R₃₀₁, R′₃₀₁, R₃₀₂ and R′₃₀₂, independently of one another, are H, OH,C₁-C₁₂alkyl; C₂-C₈alkenyl; C₁-C₁₂alkoxy; C₂-C₁₈alkenoxy; halogen;trifluoromethyl; C₇-C₁₁phenylalkyl; phenyl; phenyl which is substitutedby C₁-C₁₈alkyl, C₁-C₁₈alkoxy or halogen; phenoxy; or phenoxy which issubstituted by C₁-C₁₈alkyl, C₁-C₁₈alkoxy or halogen;R₃₀₃ and R₃₀₄, independently of one another, are H, C₁-C₁₂alkyl; OR′₃₀₇;C₂-C₆alkenyl; C₂-C₁₈alkenoxy; halogen; trifluoromethyl;C₇-C₁₁phenylalkyl; phenyl; phenyl which is substituted by C₁-C₁₈alkyl,C₁-C₁₈alkoxy or halogen; phenoxy; or phenoxy which is substituted byC₁-C₁₈alkyl, C₁-C₁₈alkoxy or halogen;R₃₀₆ is hydrogen, C₁-C₂₄alkyl, C₅-C₁₂cycloalkyl or C₇-C₁₅phenylalkyl;R₃₀₇, in the case where n=1, and R′₃₀₇, independently of one another,are hydrogen or C₁-C₁₈alkyl; or are C₁-C₁₂alkyl which is substituted byOH, C₁-C₁₈alkoxy, allyloxy, halogen, —COOH, —COOR₃₀₈, —CONH₂, —CONHR₃₀₉,—CON(R₃₀₉)(R₃₁₀), —NH₂, —NHR₃₀₉, —N(R₃₀₉)(R₃₁₀), —NHCOR₃₁₁, —CN,—OCOR₃₁₁, phenoxy and/or phenoxy which is substituted by C₁-C₁₈alkyl,C₁-C₁₈alkoxy or halogen; or R₃₀₇ is C₃-C₅₀alkyl which is interrupted by—O— and may be substituted by OH; or R₇ is C₃-C₆alkenyl; glycidyl;C₅-C₁₂cycloalkyl which is substituted by OH, C₁-C₄alkyl or —OCOR₃₁₁;C₇-C₁₁phenylalkyl which is unsubstituted or substituted by OH, Cl orCH₃; —CO—R₃₁₂ or —SO₂—R₃₁₃;R₃₀₇, in the case where n=2, is C₂-C₁₆alkylene, C₄-C₁₂alkenylene,xylylene, C₃-C₂₀alkylene which is interrupted by O and/or substituted byOH, or is a group of the formula —CH₂CH(OH)CH₂O—R₃₂₀—OCH₂CH(OH)CH₂—,—CO—R₃₂₁—CO—, —CO—NH—R₃₂₂—NH—CO— or —(CH₂)_(m)—COO—R₃₂₃—OOC—(CH₂)_(m)—in which m is a number in the range from 1 to 3, or is

R₃₀₈ is C₁-C₁₈alkyl; C₂-C₁₈alkenyl; hydroxyethyl; C₃-C₅₀alkyl which isinterrupted by O, NH, NR₃₀₉ or S and/or is substituted by OH; C₁-C₄alkylwhich is substituted by —P(O)(OR₃₁₄)₂, —N(R₃₀₉)(R₃₁₀) or —OCOR₃₁₁ and/orOH; glycidyl; C₅-C₁₂cycloalkyl; phenyl; C₇-C₁₄alkylphenyl orC₇-C₁₁phenylalkyl;R₃₀₉ and R₃₁₀, independently of one another, are C₁-C₁₂alkyl;C₃-C₁₂alkoxyalkyl; C₄-C₁₆dialkylaminoalkyl or C₅-C₁₂cycloalkyl, or R₃₀₉and R₃₁₀ together are C₃-C₉alkylene or -oxaalkylene or -azaalkylene;R₃₁₁ is C₁-C₁₈alkyl; C₂-C₁₈alkenyl or phenyl; C₂-C₁₂hydroxyalkyl;cyclohexyl; or is C₃-C₅₀alkyl which is interrupted by —O— and may besubstituted by OH;R₃₁₂ is C₁-C₁₈alkyl; C₂-C₁₈alkenyl; phenyl; C₁-C₁₈alkoxy;C₃-C₁₈alkenyloxy; C₃-C₅₀alkoxy which is interrupted by O, NH, NR₃₀₉ or Sand/or substituted by OH; cyclohexyloxy; C₇-C₁₄alkylphenoxy;C₇-C₁₁phenylalkoxy; phenoxy; C₁-C₁₂alkylamino; phenylamino; tolylaminoor naphthylamino;R₃₁₃ is C₁-C₁₂alkyl; phenyl; naphthyl or C₇-C₁₄alkylphenyl;R₃₁₄ is C₁-C₁₂alkyl, methylphenyl or phenyl;R₃₂₀ is C₂-C₁₀alkylene; C₄-C₅₀alkylene which is interrupted by O,phenylene or a -phenylene-X-phenylene- group, in which X is —O—, —S—,—SO₂—, —CH₂— or —C(CH₃)₂—;R₃₂₁ is C₂-C₁₀alkylene, C₂-C₁₀oxaalkylene, C₂-C₁₀thiaalkylene,C₆-C₁₂arylene or C₂-C₆alkenylene;R₃₂₂ is C₂-C₁₀alkylene, phenylene, tolylene, diphenylenemethane or a

group; andR₃₂₃ is C₂-C₁₀alkylene or C₄-C₂₀alkylene which is interrupted by O.

Halogen is in all cases fluorine, chlorine, bromine or iodine.

Examples of alkyl are methyl, ethyl, propyl, isopropyl, n-butyl,sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl,1-methylpentyl, 1,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl,isoheptyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl,n-octyl, 2-ethylhexyl, 1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl,nonyl, decyl, undecyl, 1-methylundecyl, dodecyl.

Examples of alkoxy having up to 12 carbon atoms are methoxy, ethoxy,propoxy, isopropoxy, butoxy, isobutoxy, pentoxy, isopentoxy, hexoxy,heptoxy, octoxy, decyloxy, dodecyloxy.

Examples of alkenoxy are propenyloxy, butenyloxy, pentenyloxy andhexenyloxy.

Examples of C₅-C₁₂cycloalkyl are cyclopentyl, cyclohexyl, cycloheptyl,cyclooctyl and cyclododecyl. C₅-C₈Cycloalkyl, especially cyclohexyl, ispreferred.

C₁-C₄Alkyl-substituted C₅-C₁₂cycloalkyl is for example methylcyclohexylor dimethylcyclohexyl.

OH— and/or C₁-C₁₀alkyl-substituted phenyl is for example methylphenyl,dimethylphenyl, trimethylphenyl, tert-butylphenyl or3,5-di-tert-butyl-4-hydroxyphenyl.

Alkoxy-substituted phenyl is for example methoxyphenyl dimethoxyphenylor trimethoxyphenyl.

Examples of C₇-C₉phenylalkyl are benzyl and phenylethyl.

C₇-C₉phenylalkyl which is substituted on the phenyl radical by —OHand/or by alkyl having up to 10 carbon atoms is for examplemethylbenzyl, dimethylbenzyl, trimethylbenzyl, tert-butylbenzyl or3,5-di-tert-butyl-4-hydroxybenzyl.

Examples of alkenyl are allyl, 2-methallyl, butenyl, pentenyl andhexenyl. Allyl is preferred. The carbon atom in position 1 is preferablysaturated.

Examples of alkylene are methylene, ethylene, propylene, trimethylene,tetramethylene, pentamethylene, 2,2-dimethyltrimethylene, hexamethylene,trimethylhexamethylene, octamethylene and decamethylene.

Examples of alkenylene are butenylene, pentenylene and hexenylene.

C₆-C₁₂ arylene is preferably phenylene.

Alkyl interrupted by O is for example —CH₂—CH₂—O—CH₂CH₃, —CH₂—CH₂—O—CH₃—or —CH₂—CH₂—O—CH₂—CH₂—CH₂—O—CH₂—CH₃—. It is preferably derived frompolyethlene glycol. A general description is —((CH₂)_(a)—O)_(b)—H/CH₃,wherein a is a number from 1 to 6 and b is a number from 2 to 10.

C₂-C₁₀ oxaalkylene and C₂-C₁₀thiaalkylene can be deduced from the abovementioned alkylene groups by substituting one or more carbon atoms by anoxygen atom or a sulphur atom.

Specific examples of 2-hydroxybenzophenones are for example the4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy; 4-dodecyloxy, 4-benzyloxyand 2′-hydroxy-4,4′-dimethoxy derivatives.

Specific examples of 2-(2′-hydroxyphenyl)benzotriazoles are for example2-(2′-hydroxy-5′-methylphenyl)-benzotriazole,2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(5′-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(2′-hydroxy-5′-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole,2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)-5-chloro-benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-methylphenyl)-5-chloro-benzotriazole,2-(3′-sec-butyl-5′-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(2′-hydroxy-4′-octyloxyphenyl)benzotriazole,2-(3′,5′-di-tert-amyl-2′-hydroxyphenyl)benzotriazole,2-(3′,5′-bis-(α,α-dimethylbenzyl)-2′-hydroxyphenyl)benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)-5-chloro-benzotriazole,2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy)-carbonylethyl]-2′-hydroxyphenyl)-5-chloro-benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)-5-chloro-benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)benzotriazole,2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy)carbonylethyl]-2′-hydroxyphenyl)benzotriazole,2-(3′-dodecyl-2′-hydroxy-5′-methylphenyl)benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-isooctyloxycarbonylethyl)phenylbenzotriazole,2,2′-methylene-bis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazole-2-ylphenol];the transesterification product of2-[3′-tert-butyl-5′-(2-methoxycarbonylethyl)-2′-hydroxyphenyl]-2H-benzotriazolewith polyethylene glycol 300; [R—CH₂CH₂—COO—CH₂CH₂

₂ where R=3′-tert-butyl-4′-hydroxy-5′-2H-benzotriazol-2-ylphenyl,2-[2′-hydroxy-3′-(α,α-dimethylbenzyl)-5′-(1,1,3,3-tetramethylbutyl)-phenyl]benzotriazole;2-[2′-hydroxy-3′-(1,1,3,3-tetramethylbutyl)-5′-(α,αdimethylbenzyl)-phenyl]benzotriazole.

Specific examples of 2-(2-hydroxyphenyl)-1,3,5-triazines are for example2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2,4-bis(2-hydroxypropyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-butyloxy-propoxy)phenyl]-4,6-bis(2,4-dimethylyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-octyloxy-propyloxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine,2-[4-(dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-4-dodecyloxypropoxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1,3,5-triazine,2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine,2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxy-propoxy)phenyl]-1,3,5-triazine,2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-4,6-phenyl-1,3,5-triazine,2-{2-hydroxy-4-[3-(2-ethylhexyl-1-oxy)-2-hydroxy-propyloxy]phenyl}-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazineand2-(2-hydroxy-4-(2-ethylhexyl)oxy)phenyl-4,6-di(4-phenyl)phenyl-1,3,5-triazine.

For instance the hydroxyphenyl-triazine UV-absorbers are of formulae:

The hydroxyphenyl triazine UV-absorbers are known and partially items ofcommerce. They can be prepared according to the above documents.

Specific examples for oxamides are for example 4,4′-dioctyloxyoxanilide,2,2′-diethoxyoxanilide, 2,2′-dioctyloxy-5,5′-di-tert-butoxanilide,2,2′-didodecyloxy-5,5′-di-tert-butoxanilide, 2-ethoxy-2′-ethyloxanilide,N,N′-bis(3-dimethylaminopropyl)oxamide,2-ethoxy-5-tert-butyl-2′-ethoxanilide and its mixture with2-ethoxy-2′-ethyl-5,4′-di-tert-butoxanilide, mixtures of o- andp-methoxy-disubstituted oxanilides and mixtures of o- andp-ethoxy-disubstituted oxanilides.

The above mentioned UV-absorbers are largely items of commerce and forexample known as Tinuvin® 109, 171, 326, 327, 328, 350, 360, 384, 400,405, 411 or Chimassorb® 81 from Ciba Specialty Chemicals or Cyasorb®1164 from Cytech Inc.

In many cases it may be of advantage to use a combination ofUV-absorbers from different classes, such as for example a benzophenoneUV-absorber with a benzotriazole UV-absorber or a hydroxyphenyltriazineUV-absorber with a benzotriazole UV-absorber. If such a combination isused, the weight ratio between both UV-absorbers is for example from 1:5to 5:1, for instance from 1:3 to 3:1, particularly 1:1.5 to 1.5:1.

The sterically hindered amine contains at least one radical of theformula

in which R is hydrogen or methyl.

The sterically hindered amine light stabilizer useful in the instantinvention is preferably a compound of formulae (A-1) to (A-10) or offormulae (B-1) to (B-10);

(α-1) a compound of the formula (A-1)

in whichE₁ is hydrogen, C₁-C₈alkyl, O., —OH, —CH₂CN, C₁-C₁₈alkoxy,C₅-C₁₂cycloalkoxy, C₃-C₆alkenyl, C₇-C₉phenylalkyl unsubstituted orsubstituted on the phenyl by 1, 2 or 3 C₁-C₄alkyl; or C₁-C₈acyl,m₁ is 1, 2 or 4,if m₁ is 1, E₂ is C₁-C₂₅alkyl,if m₁ is 2, E₂ is C₁-C₁₄alkylene or a group of the formula (a-I)

wherein E₃ is C₁-C₁₀alkyl or C₂₋₁₀alkenyl, E₄ is C₁-C₁₀alkylene, andE₅ and E₆ independently of one another are C₁-C₄alkyl, cyclohexyl ormethylcyclohexyl, andif m₁ is 4, E₂ is C₄-C₁₀alkanetetrayl;(α-2) a compound of the formula (A-2)

in whichtwo of the radicals E₇ are —COO—(C₁-C₂₀alkyl), andtwo of the radicals E₇ are a group of the formula (a-II)

with E₈ having one of the meanings of E₁;(α-3) a compound of the formula (A-3)

in whichE₉ and E₁₀ together form C₂-C₁₄alkylene,E₁₁ is hydrogen or a group —Z₁—COO—Z₂,Z₁ is C₂-C₁₄alkylene, andZ₂ is C₁-C₂₄alkyl, andE₁₂ has one of the meanings of E₁;(α-4) a compound of the formula (A-4)

whereinthe radicals E₁₃ independently of one another have one of the meaningsof E₁,the radicals E₁₄ independently of one another are hydrogen orC₁-C₁₂alkyl, andE₁₅ is C₁-C₁₀alkylene or C₃-C₁₀alkylidene;(α-5) a compound of the formula (A-5)

whereinthe radicals E₁₆ independently of one another have one of the meaningsof E₁;(α-6) a compound of the formula (A-6)

in whichE₁₇ is C₁-C₂₄alkyl, andE₁₈ has one of the meanings of E₁;(α-7) a compound of the formula (A-7)

in whichE₁₉, E₂₀ and E₂₁ independently of one another are a group of the formula(a-III)

wherein E₂₂ has one of the meanings of E₁;(α-8) a compound of the formula (A-8)

whereinthe radicals E₂₃ independently of one another have one of the meaningsof E₁,and E₂₄ is hydrogen, C₁-C₁₂alkyl or C₁-C₁₂alkoxy;(α-9) a compound of the formula (A-9)

whereinm₂ is 1, 2 or 3,E₂₅ has one of the meanings of E₁, andwhen m₂ is 1, E₂₆ is a group

when m₂ is 2, E₂₆ is C₂-C₂₂alkylene, andwhen m₂ is 3, E₂₈ is a group of the formula (a-IV)

wherein the radicals E₂₇ independently of one another areC₂-C₁₂alkylene, and the radicals E₂₈ independently of one another areC₁-C₁₂alkyl or C₅-C₁₂cycloalkyl;(α-10) a compound of the formula (A-10)

whereinthe radicals E₂₉ independently of one another have one of the meaningsof E₁, andE₃₀ is C₂-C₂₂alkylene, C₅-C₇cycloalkylene,C₁-C₄alkylenedi(C₅-C₇cycloalkylene), phenylene orphenylenedi(C₁-C₄alkylene);(β-1) a compound of the formula (B-1)

in whichR₂₀₁, R₂₀₃, R₂₀₄ and R₂₀₅ independently of one another are hydrogen,C₁-C₁₂alkyl, C₅-C₁₂cycloalkyl, C₁-C₄-alkyl-substituted C₅-C₁₂cycloalkyl,phenyl, phenyl which is substituted by —OH and/or C₁-C₁₀alkyl;C₇-C₉phenylalkyl, C₇-C₉phenylalkyl which is substituted on the phenylradical by —OH and/or C₁-C₁₀alkyl; or a group of the formula (b-I)

R₂₀₂ is C₂-C₁₈alkylene, C₅-C₇cycloalkylene orC₁-C₄alkylenedi(B₅—C₇cycloalkylene),orthe radicals R₂₀₁, R₂₀₂ and R₂₀₃, together with the nitrogen atoms towhich they are bonded, perform a 5- to 10-membered heterocyclic ring, orR₂₀₄ and R₂₀₅, together with the nitrogen atom to which they are bonded,form a 5- to 10-membered heterocyclic ring,R₂₀₆ is hydrogen, C₁-C₈alkyl, O., —OH, —CH₂CN, C₁-C₁₈alkoxy,C₅-C₁₂cycloalkoxy, C₃-C₆alkenyl, C₇-C₉phenylalkyl unsubstituted orsubstituted on the phenyl by 1, 2 or 3 C₁-C₄alkyl; or C₁-C₈acyl, andb₁ is a number from 2 to 50,with the proviso that at least one of the radicals R₂₀₁, R₂₀₃, R₂₀₄ andR₂₀₅ is a group of the formula (b-I);(β-2) a compound of the formula (B-2)

whereinR₂₀₇ and R₂₁₁ independently of one another are hydrogen or C₁-C₁₂alkyl,R₂₀₈, R₂₀₉ and R₂₁₀ independently of one another are C₂-C₁₀alkylene, andX₁, X₂, X₃, X₄, X₅, X₆, X₇ and X₈ independently of one another are agroup of the formula (b-II),

in which R₂₁₂ is hydrogen, C₁-C₁₂alkyl, C₅-C₁₂cycloalkyl,C₁-C₄alkyl-substituted C₅-C₁₂cycloalkyl, phenyl, —OH— and/orC₁-C₁₀alkyl-substituted phenyl, C₇-C₉phenylalkyl, C₇-C₉phenylalkyl whichis substituted on the phenyl radical by —OH and/or C₁-C₁₀alkyl; or agroup of the formula (b-I) as defined above, andR₂₁₃ has one of the meanings of R₂₀₈;(β-3) a compound of the formula (B-3)

in whichR₂₁₄ is C₁-C₁₀alkyl, C₅-C₁₂cycloalkyl, C₁-C₄alkyl-substitutedC₅-C₁₂cycloalkyl, phenyl or C₁-C₁₀alkyl-substituted phenyl,R₂₁₅ is C₃-C₁₀alkylene,R₂₁₆ has one of the meanings of R₂₀₆, andb₂ is a number from 2 to 50;(β1-4) a compound of the formula (B-4)

in whichR₂₁₇ and R₂₂₁ independently of one another are a direct bond or a—N(X₉)—CO—X₁₀—CO—N(X₁₁)— group, where X₉ and X₁₁, independently of oneanother are hydrogen, C₁-C₈alkyl, C₅-C₁₂cycloalkyl, phenyl,C₇-C₉phenylalkyl or a group of the formula (b-I),X₁₀ is a direct bond or C₁-C₄alkylene,R₂₁₈ has one of the meanings of R₂₀₆,R₂₁₉, R₂₂₀, R₂₂₃ and R₂₂₄ independently of one another are hydrogen,C₁-C₃₀alkyl, C₅-C₁₂cycloalkyl or phenyl,R₂₂₂ is hydrogen, C₁-C₃₀alkyl, C₅-C₁₂cycloalkyl, phenyl,C₇-C₉phenylalkyl or a group of the formula (b-I), andb₃ is a number from 1 to 50;(β-5) a compound of the formula (B-5)

R₂₂₅, R₂₂₆, R₂₂₇, R₂₂₈ and R₂₂₉ independently of one another are adirect bond or C₁-C₁₀alkylene,R₂₃₀ has one of the meanings of R₂₀₈, andb₄ is a number from 1 to 50;(β-6) a product (B-6) obtainable by reacting a product, obtained byreaction of a polyamine of the formula (B-6-1) with cyanuric chloride,with a compound of the formula (B-6-2)

in whichb′₅, b″₅ and b′″₅ independently of one another are a number from 2 to12,R₂₃₁ is hydrogen, C₁-C₁₂alkyl, C₅-C₁₂cycloalkyl, phenyl orC₇-C₉phenylalkyl, andR₂₃₂ has one of the meanings of R₂₀₆;(β-7) a compound of the formula (B-7)

wherein A₁ is hydrogen or C₁-C₄alkyl,A₂ is a direct bond or C₁-C₁₀alkylene, andn₁ is a number from 2 to 50;(β-8) at least one compound of the formulae (B-8-a) and (B-8-b)

wherein n₂ and n₂* are a number from 2 to 50;(β-9) a compound of the formula (B-9)

wherein A₃ and A₄ independently of one another are hydrogen orC₁-C₈alkyl, or A₃ and A₄ together form a C₂-C₁₄alkylene group, andthe variables n₃ independently of one another are a number from 1 to 50;and(β-10) a compound of the formula (B-10)

wherein n₄ is a number from 2 to 50,A₅ is hydrogen or C₁-C₄alkyl,the radicals A₆ and A₇ independently of one another are C₁-C₄alkyl or agroup of the formula (b-I), with the proviso that at least 50% of theradicals A₇ are a group of the formula (b-I).

Examples of alkyl having up to 30 carbon atoms are methyl, ethyl,propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl,2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl, 1,3-dimethylbutyl,n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl,1-methylheptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl,1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl, decyl, undecyl,1-methylundecyl, dodecyl, 1,1,3,3,5,5-hexamethylhexyl, tridecyl,tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, eicosyl,docosyl and triacontyl. One of the preferred definitions of E₁, E₈, E₁₂,E₁₃, E₁₆, E₁₈, E₂₂, E₂₃, E₂₅, E₂₉, R₂₀₆, R₂₁₃, R₂₁₆, R₂₁₈, R₂₃₀ and R₂₃₂is C₁-C₄alkyl, especially methyl. R₂₃₁ is preferably butyl.

Examples of alkoxy having up to 18 carbon atoms are methoxy, ethoxy,propoxy, isopropoxy, butoxy, isobutoxy, pentoxy, isopentoxy, hexoxy,heptoxy, octoxy, decyloxy, dodecyloxy, tetradecyloxy, hexadecyloxy andoctadecyloxy. One of the preferred meanings of E₁ is octoxy. E₂₄ ispreferably C₁-C₄alkoxy and one of the preferred meanings of R₂₀₆ ispropoxy.

Examples of C₅-C₁₂cycloalkyl are cyclopentyl, cyclohexyl, cycloheptyl,cyclooctyl and cyclododecyl. C₅-C₈Cycloalkyl, especially cyclohexyl, ispreferred.

C₁-C₄Alkyl-substituted C₅-C₁₂cycloalkyl is for example methylcyclohexylor dimethylcyclohexyl.

Examples of C₅-C₁₂cycloalkoxy are cyclopentoxy, cyclohexoxy,cycloheptoxy, cyclooctoxy, cyclodecyloxy and cyclododecyloxy.C₅-C₈Cycloalkoxy, in particular cyclopentoxy and cyclohexoxy, ispreferred.

—OH— and/or C₁-C₁₀alkyl-substituted phenyl is for example methylphenyl,dimethylphenyl, trimethylphenyl, tert-butylphenyl or3,5-di-tert-butyl-4-hydroxyphenyl.

Examples of C₇-C₉phenylalkyl are benzyl and phenylethyl.

C₇-C₉phenylalkyl which is substituted on the phenyl radical by —OHand/or by alkyl having up to 10 carbon atoms is for examplemethylbenzyl, dimethylbenzyl, trimethylbenzyl, tert-butylbenzyl or3,5-di-tert-butyl-4-hydroxybenzyl.

Examples of alkenyl having up to 10 carbon atoms are allyl, 2-methallyl,butenyl, pentenyl and hexenyl. Allyl is preferred. The carbon atom inposition 1 is preferably saturated.

Examples of acyl containing not more than 8 carbon atoms are formyl,acetyl, propionyl, butyryl, pentanoyl, hexanoyl, heptanoyl, octanoyl,acryloyl, methacryloyl and benzoyl. C₁-C₈Alkanoyl, C₃-C₈alkenyl andbenzoyl are preferred. Acetyl and acryloyl are especially preferred.

Examples of alkylene having up to 22 carbon atoms are methylene,ethylene, propylene, trimethylene, tetramethylene, pentamethylene,2,2-dimethyltrimethylene, hexamethylene, trimethylhexamethylene,octamethylene and decamethylene.

An example of C₃-C₁₀alkylidene is the group

An example of C₄-C₁₀alkanetetrayl is 1,2,3,4-butanetetrayl.

An example of C₅-C₇cycloalkylene is cyclohexylene.

An example of C₁-C₄alkylenedi(C₅-C₇cycloalkylene) ismethylenedicyclohexylene.

An example of phenylenedi(C₁-C₄alkylene) ismethylene-phenylene-methylene or ethylene-phenylene-ethylene.

Where the radicals R₂₀₁, R₂₀₂ and R₂₀₃, together with the nitrogen atomsto which they are attached, form a 5- to 10-membered heterocyclic ring,this ring is for example

A 6-membered heterocyclic ring is preferred.

Where the radicals R₂₀₄ and R₂₀₅, together with the nitrogen atom towhich they are attached, form a 5- to 10-membered heterocyclic ring,this ring is for example 1-pyrrolidyl, piperidino, morpholino,1-piperazinyl, 4-methyl-1-piperazinyl, 1-hexahydroazepinyl,5,5,7-trimethyl-1-homopiperazinyl or4,5,5,7-tetramethyl-1-homopiperazinyl. Morpholino is particularlypreferred.

One of the preferred definitions of R₂₁₉ and R₂₂₃ is phenyl.

R₂₂₆ is preferably a direct bond.

n₁, n₂, n₂* and n₄ are preferably a number from 2 to 25, in particular 2to 20.

n₃ is preferably a number from 1 to 25, in particular 1 to 20.

b₁ and b₂ are preferably a number from 2 to 25, in particular 2 to 20.

b₃ and b₄ are preferably a number from 1 to 25, in particular 1 to 20.

b′₅ and b′″₅ are preferably 3 and b″₅ is preferably 2.

The compounds described above are essentially known and commerciallyavailable. All of them can be prepared by known processes.

The preparation of the compounds is disclosed, for example, in U.S. Pat.No. 5,679,733, U.S. Pat. No. 3,640,928, U.S. Pat. No. 4,198,334, U.S.Pat. No. 5,204,473, U.S. Pat. No. 4,619,958, U.S. Pat. No. 4,110,306,U.S. Pat. No. 4,110,334, U.S. Pat. No. 4,689,416, U.S. Pat. No.4,408,051, U.S. Pat. No. 768,175 (Derwent 88-138,751/20), U.S. Pat. No.5,049,604, U.S. Pat. No. 4,769,457, U.S. Pat. No. 4,356,307, U.S. Pat.No. 4,619,956, U.S. Pat. No. 5,182,390, GB-A-2,269,819, U.S. Pat. No.4,292,240, U.S. Pat. No. 5,026,849, U.S. Pat. No. 5,071,981, U.S. Pat.No. 4,547,538, U.S. Pat. No. 4,976,889, U.S. Pat. No. 4,086,204, U.S.Pat. No. 6,046,304, U.S. Pat. No. 4,331,586, U.S. Pat. No. 4,108,829,U.S. Pat. No. 5,051,458, WO-A-94/12,544 (Derwent 94-177,274/22),DD-A-262,439 (Derwent 89-122,983/17), U.S. Pat. No. 4,857,595, U.S. Pat.No. 4,529,760, U.S. Pat. No. 4,477,615, CAS 136,504-96-6, U.S. Pat. No.4,233,412, U.S. Pat. No. 4,340,534, WO-A-98/51,690 and EP-A-1,803.

The product (B-6) can be prepared analogously to known processes, forexample by reacting a polyamine of formula (B-6-1) with cyanuricchloride in a molar ratio of from 1:2 to 1:4 in the presence ofanhydrous lithium carbonate, sodium carbonate or potassium carbonate inan organic solvent such as 1,2-dichloroethane, toluene, xylene, benzene,dioxane or tert-amyl alcohol at a temperature of from −20° C. to +10°C., preferably from −10° C. to +10° C., in particular from 0° C. to +10°C., for from 2 to 8 hours, followed by reaction of the resultant productwith a 2,2,6,6-tetramethyl-4-piperidylamine of the formula (B-6-2). Themolar ratio of the 2,2,6,6-tetramethyl-4-piperidylamine to polyamine ofthe formula (B-6-1) employed is for example from 4:1 to 8:1. Thequantity of the 2,2,6,6-tetramethyl-4-piperidylamine can be added in oneportion or in more than one portion at intervals of a few hours.

The molar ratio of polyamine of the formula (B-6-1) to cyanuric chlorideto 2,2,6,6-tetramethyl-4-piperidylamine of the formula (B-6-2) ispreferably from 1:3:5 to 1:3:6.

The following example indicates one way of preparing a preferred product(B-6-a).

Example: 23.6 g (0.128 mol) of cyanuric chloride, 7.43 g (0.0426 mol) ofN,N′-bis[3-aminopropyl]ethylenediamine and 18 g (0.13 mol) of anhydrouspotassium carbonate are reacted at 5° C. for 3 hours with stirring in250 ml of 1,2-dichloroethane. The mixture is warmed at room temperaturefor a further 4 hours. 27.2 g (0.128 mol) ofN-(2,2,6,6-tetramethyl-4-piperidyl)butylamine are added and theresultant mixture is warmed at 60° C. for 2 hours. A further 18 g (0.13mol) of anhydrous potassium carbonate are added and the mixture iswarmed at 60° C. for a further 6 hours. The solvent is removed bydistillation under a slight vacuum (200 mbar) and replaced by xylene.18.2 g (0.085 mol) of N-(2,2,6,6-tetramethyl-4-piperidyl)butylamine and5.2 g (0.13 mol) of ground sodium hydroxide are added, the mixture isheated at reflux for 2 hours and, for a further 12 hours, the waterformed during the reaction is removed by azeotropic distillation. Themixture is filtered. The solution is washed with water and dried overNa₂SO₄. The solvent is evaporated and the residue is dried at 120-130°C. in vacuo (0.1 mbar). The desired product is obtained as a colourlessresin.

In general, the product (B-6) can, for example, be represented by acompound of the formula (B-6-α), (B-6-β) or (B-6-γ). It can also be inthe form of a mixture of these three compounds.

A preferred meaning of the formula (B-6-α) is

A preferred meaning of the formula (B-6-β) is

A preferred meaning of the formula (B-6-γ) is

In the above formulae (B-6-α) to (B-6-γ), b₅ is preferably 2 to 20, inparticular 2 to 10.

The sterically hindered amine compounds of component (c) are preferablyselected from the group consisting of the following commercial products:DASTIB 845®, TINUVIN 770®, TINUVIN NOR 371®, TINUVIN 765®, TINUVIN 144®,TINUVIN 123®, TINUVIN 111®, TINUVIN 783®, TINUVIN 791®, MARK LA 52®,MARK LA 57®, MARK LA 62®, MARK LA 67®, HOSTAVIN N 20®, HOSTAVIN N 24®,SANDUVOR 3050®, SANDUVOR 3053®, SANDUVOR 3058®, DIACETAM 5®,SUMISORB™61®, UVINUL 4049®, SANDUVOR PR 31®, GOODRITE UV 3034®, GOODRITEUV 3150®, GOODRITE UV 3159®, GOODRITE 3110×128®, UVINUL 4050H®,CHIMASSORB 944®, CHIMASSORB 2020®, CYASORB UV 3346®, CYASORB UV 3529®,DASTIB 1082®, CHIMASSORB 119®, UVASIL 299®, UVASIL 125®, UVASIL 2000®,UVINUL 5050H®, LICHTSCHUTZSTOFF UV 31®, LUCHEM HA B 18®, MARK LA 63®,MARK LA 68®, UVASORB HA 88®, TINUVIN 622®, HOSTAVIN N 30® and FERRO AM806®.

Particularly preferred are TINUVIN 770®, TINUVIN NOR 371®, TINUVIN 791®,TINUVIN 622®, TINUVIN 783®, CHIMASSORB 944®, CHIMASSORB 2020® andCHIMASSORB 119®.

Most preferred are Tinuvin 770®, TINUVIN 292®, TINUVIN 123®, TINUVIN152®, TINUVIN NOR 371® and TINUVIN 791®.

The meanings of the terminal groups which saturate the free valences inthe compounds of the formulae (B-1), (B-3), (B-4), (B-5), (B-6-α),(B-6-β), (B-6-γ), (B-7), (B-8-a), (B-8-b) and (B-10) depend on theprocesses used for their preparation. The terminal groups can also bemodified after the preparation of the compounds.

If the compounds of the formula (B-1) are prepared by reacting acompound of the formula

in which X is, for example, halogen, in particular chlorine, and R₂₀₄and R₂₀₅ are as defined above, with a compound of the formula

in which R₂₀₁, R₂₀₂ and R₂₀₃ are as defined above, the terminal groupbonded to the diamino radical is hydrogen or

and the terminal group bonded to the triazine radical is X or

If X is halogen, it is advantageous to replace this, for example, by —OHor an amino group when the reaction is complete. Examples of aminogroups which may be mentioned are pyrrolidin-1-yl, morpholino, —NH₂,—N(C₁-C₈)alkyl)₂ and —NR(C₁-C₈alkyl), in which R is hydrogen or a groupof the formula (b-I).

The compounds of the formula (B-1) also cover compounds of the formula

wherein R₂₀₁, R₂₀₂, R₂₀₃, R₂₀₄, R₂₀₅ and b₁ are as defined above andR₂₀₄* has one of the meanings of R₂₀₄ and R₂₀₅* has one of the meaningsof R₂₀₅.

One of the particularly preferred compounds of the formula (B-1) is

The preparation of this compound is described in Example 10 of U.S. Pat.No. 6,046,304.

In the compounds of the formula (B-3), the terminal group bonded to thesilicon atom can be, for example, (R₁₄)₃Si—O—, and the terminal groupbonded to the oxygen can be, for example, —Si(R₁₄)₃.

The compounds of the formula (B-3) can also be in the form of cycliccompounds if b₂ is a number from 3 to 10, i.e. the free valences shownin the structural formula then form a direct bond.

In the compounds of the formula (B-4), the terminal group bonded to the2,5-dioxopyrrolidine ring is, for example, hydrogen, and the terminalgroup bonded to the —C(R₂₂₃)(R₂₂₄)— radical is, for example,

In the compounds of the formula (B-5), the terminal group bonded to thecarbonyl radical is, for example,

and the terminal group bonded to the oxygen radical is, for example,

In the compounds of the formulae (B-6-α), (B-6-β) and (B-6-γ), theterminal group bonded to the triazine radical is, for example, Cl or a

group, and the terminal group bonded to the amino radical is, forexample, hydrogen or a

group.

If the compounds of the formula (B-7) are prepared, for example, byreacting a compound of the formula

in which A₁ is hydrogen or methyl, with a dicarboxylic acid diester ofthe formula Y—OOC-A₂-COO—Y, in which Y is, for example, methyl, ethyl orpropyl, and A₂ is as defined above, the terminal group bonded to the2,2,6,6-tetramethyl-4-oxypiperidin-1-yl radical is hydrogen or—CO-A₂-COO—Y, and the terminal group bonded to the diacyl radical is—O—Y or

In the compounds of the formula (B-8-a), the terminal group bonded tothe nitrogen can be, for example, hydrogen and the terminal group bondedto the 2-hydroxypropylene radical can be, for example, a

group.

In the compounds of the formula (B-8-b), the terminal group bonded tothe dimethylene radical can be, for example, —OH, and the terminal groupbonded to the oxygen can be, for example, hydrogen. The terminal groupscan also be polyether radicals.

In the compounds of the formula (B-10), the end group bonded to the—CH₂— residue can be, for example, hydrogen and the end group bonded tothe —CH(CO₂A₇) residue can be, for example, —CH═CH—COOA₇.

Specific examples for the sterically hindered amines arebis(2,2,6,6-tetramethyl-4-piperidyl)sebacate,bis(2,2,6,6-tetramethyl-4-piperidyl)succinate,bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate,bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate,bis(1,2,2,6,6-pentamethyl-4-piperidyl)n-butyl-3,5-di-tert-butylhydroxybenzylmalonate, the condensate of1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinicacid, linear or cyclic condensates ofN,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-tert-octylamino-2,6-dichloro-1,3,5-triazine,tris(2,2,6,6-tetramethyl-4-piperidyl)nitrilotriacetate,tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butane-tetracarboxylate,1,1′-(1,2-ethanediyl) bis(3,3,5,5-tetramethylpiperazinone),4-benzoyl-2,2,6,6-tetramethylpiperidine,4-stearyloxy-2,2,6,6-tetramethylpiperidine,bis(1,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)malonate,3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decan-2,4-dione,bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)succinate, linear or cycliccondensates ofN,N′-bis-(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-morpholino-2,6-dichloro-1,3,5-triazine, the condensate of2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triazineand 1,2-bis(3-aminopropylamino)ethane, the condensate of2-chloro-4,6-di-(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-triazineand 1,2-bis-(3-aminopropylamino)ethane,8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]-decane-2,4-dione,3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidin-2,5-dione,3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidyl)pyrrolidine-2,5-dione, amixture of 4-hexadecyloxy- and4-stearyloxy-2,2,6,6-tetramethylpiperidine, a condensation product ofN,N′-bis(2,2,6,6-tetramethylpiperidyl)hexamethylenediamine and4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, a condensation product of1,2-bis(3-aminopropylamino)ethane and 2,4,6-trichloro-1,3,5-triazine aswell as 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No.[136504-96-6]);N-(2,2,6,6-tetramethyl-4-piperidyl)-n-dodecylsuccinimide,N-(1,2,2,6,6-pentamethyl-4-piperidyl)-n-dodecylsuccinimide,2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro[4,5]decane, areaction product of7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro[4,5]decaneund epichlorohydrin,1,1-bis(1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl)-2-(4-methoxyphenyl)ethene,N,N′-bis-formyl-N,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine,diester of 4-methoxy-methylene-malonic acid with1,2,2,6,6-pentamethyl-4-hydroxypiperidine,poly[methylpropyl-3-oxy-4-(2,2,6,6-tetramethyl-4-piperidyl)]siloxane andreaction product of maleic acid anhydride-α-olefin-copolymer with2,2,6,6-tetramethyl-4-aminopiperidine,1,2,2,6,6-pentamethyl-4-aminopiperidine,2,4-bis[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidine-4-yl)-N-butyl-amino]-6-(2-hydroxyethyl)-amino-1,3,5-triazine,1-(2-Hydroxy-2-methylpropoxy)-4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine,5-(2-ethylhexanoyl)oxymethyl-3,3,5-trimethyl-2-morpholinone or acompound

in which n is from 1 to 15, disclosed in example 2 of U.S. Pat. No.6,117,995.

The sterically hindered amines mentioned above are known and are largelyitems of commerce.

A further aspect of the invention is a process for the preparation of aconcentrated aqueous polymer dispersion with an average particle size ofless than 1000 nm comprising the step polymerizing at least oneethylenically unsaturated monomer in the presence of a non-polar organiclight stabilizer by heterophase radical polymerization;

wherein the weight ratio of non-polar organic light stabilizer topolymer carrier formed from the ethylenically unsaturated monomer isgreater than 50 parts of light stabilizer per 100 parts of polymercarrier.

In a specific embodiment of the invention the process for thepreparation of a concentrated aqueous polymer dispersion comprises thesteps

-   -   a) dissolving, emulsifying or dispersing a non-polar organic        light stabilizer in at least one ethylenically unsaturated        monomer;    -   b) preparing a conventional oil in water emulsion of said light        stabilizer dissolved, emulsified or dispersed in at least one        ethylenically unsaturated monomer;    -   c) homogenizing the conventional emulsion to a miniemulsion        wherein the droplets of the organic phase have an average        diameter below 1000 nm;    -   d) polymerizing the miniemulsion by adding a polymerization        initiator;        wherein the weight ratio of non-polar organic light stabilizer        to polymer carrier formed from the ethylenically unsaturated        monomer is greater than 50 parts of light stabilizer per 100        parts of polymer carrier.

In step b) preferably a non-ionic, cationic or anionic surfactant isadditionally present.

In general anionic and non-ionic surfactants are preferred.

Optionally other water miscible solvents may be present usually lessthan 10% by weight based on the water content. Exemplary cosolventsuseful in the present invention may be selected from the groupconsisting of aliphatic alcohols, glycols, ethers, glycol ethers,pyrrolidines, N-alkyl pyrrolidinones, N-alkyl pyrrolidones, polyethyleneglycols, polypropylene glycols, amides, carboxylic acids and saltsthereof, esters, organosulfides, sulfoxides, sulfones, alcoholderivatives, hydroxyether derivatives such as butyl carbitol orcellosolve, amino alcohols, ketones, and the like, as well asderivatives thereof and mixtures thereof. Specific examples includemethanol, ethanol, propanol, dioxane, ethylene glycol, propylene glycol,diethylene glycol, glycerol, dipropylene glycol, tetrahydrofuran, andother water-soluble or water-miscible materials, and mixtures thereof.

Preferred are water, water alcohol mixtures, water ethylene glycol orpropylene glycol mixtures, water acetone, water tetrahydrofurane, orwater dimethylformamide mixtures.

Suitable surfactants or surface active compounds, which may be added areknown in the art. The amounts typically used range from 0.01% by weightto 10% by weight, based on the monomer or monomers.

Typical surfactants useful in the present invention are of nonionic,cationic or anionic type.

Examples for anionic surfactants are alkali and ammonium salts ofC₁₂-C₁₈alkylsulfonic acid, dialkyl esters of succinic acid or sulfuricacid halfesters of ethoxylated alkanoles. These compounds are known forexample from U.S. Pat. No. 4,269,749 and largely items of commerce, suchas under the trade name Dowfax® 2A1 (Dow Chemical Company).

Nonionic surfactants are for example aliphatic or araliphatic compoundssuch as ethoxylated phenols (mon, di, tri) with an ethoxylation degreeof 3 to 50 and alkyl groups in the range from C₄-C₉, ethoxylated longchain alcohols or polyethyleneoxide/polypropyleneoxide block copolymers.

Furthermore protective colloids such as polyvinylalcohols, starch,cellulose derivatives or copolymers containing vinylpyrrolidone may beadded to form a conventional oil in water emulsion according to step b).Further examples are given in “Houben-Weyl, Methoden der OrganischenChemie, Band XIV/1, Makromolekulare Stoffe, G. Thieme Verlag Stuttgart1961, 411-420”.

The homogenization step b) and c) is usually carried out by applyingmechanical agitation (rotor/stator disperser) followed by using highforce dispersion devices like for example a ultrasonic sound equipment(J. Dispersion Sci. Technology 2002, 23(1-3), 333-349) or a highpressure homogenizer (APV Gaulin homogenizer; Microfluidizer) Theemulsification/homogenization can be carried out continuously orbatchwise. Apparatus for this purpose are known in the art. This is forexample described in U.S. Pat. No. 5,108,654.

The polymerization step d) is carried out by adding a free radicalpolymerization initiator.

Preferably the free radical initiator is present in an amount of from0.01 weight-% to 20 weight-%, more preferably from 0.1 weight-% to 10weight-% and most preferably from 0.2 weight-% to 5 weight-%, based onthe monomer or monomer mixture.

The polymerization initiator may be added batchwise or continuously tothe reaction mixture.

Preferably the free radical initiator of component b) is a bis-azocompound, a peroxide or a hydroperoxide.

Specific preferred radical sources are 2,2′-azobisisobutyronitrile,2,2′-azobis(2-methyl-butyronitrile),2,2′-azobis(2,4-dimethylvaleronitrile),2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile),1,1′-azobis(1-cyclohexanecarbonitrile),2,2′-azobis(isobutyramide)dihydrate,2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile,dimethyl-2,2′-azobisisobutyrate, 2-(carbamoylazo)isobutyronitrile,2,2′-azobis(2,4,4-trimethylpentane), 2,2′-azobis(2-methylpropane),2,2′-azobis(N,N′-dimethyleneisobutyramidine), free base orhydrochloride, 2,2′-azobis(2-amidinopropane), free base orhydrochloride,2,2′-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)ethyl]propionamide} or2,2′-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide;acetyl cyclohexane sulphonyl peroxide, diisopropyl peroxy dicarbonate,t-amyl perneodecanoate, t-butyl perneodecanoate, t-butyl perpivalate,t-amylperpivalate, bis(2,4-dichlorobenzoyl)peroxide, diisononanoylperoxide, didecanoyl peroxide, dioctanoyl peroxide, dilauroyl peroxide,bis(2-methylbenzoyl) peroxide, disuccinic acid peroxide, diacetylperoxide, dibenzoyl peroxide, t-butyl per 2-ethylhexanoate,bis-(4-chlorobenzoyl)-peroxide, t-butyl perisobutyrate, t-butylpermaleinate, 1,1-bis(t-butylperoxy) 3,5,5-trimethylcyclohexane,1,1-bis(t-butylperoxy)cyclohexane, t-butyl peroxy isopropyl carbonate,t-butyl perisononaoate, 2,5-dimethylhexane 2,5-dibenzoate, t-butylperacetate, t-amyl perbenzoate, t-butyl perbenzoate,2,2-bis(t-butylperoxy)butane, 2,2 bis (t-butylperoxy)propane, dicumylperoxide, 2,5-dimethylhexane-2,5-di-t-butylperoxide, 3-t-butylperoxy3-phenylphthalide, di-t-amyl peroxide, α,α′-bis(t-butylperoxyisopropyl)benzene, 3,5-bis(t-butylperoxy)3,5-dimethyl 1,2-dioxolane,di-t-butyl peroxide, 2,5-dimethylhexyne-2,5-di-t-butylperoxide,3,3,6,6,9,9-hexamethyl 1,2,4,5-tetraoxa cyclononane, p-menthanehydroperoxide, pinane hydroperoxide, diisopropylbenzenemono-α-hydroperoxide, cumene hydroperoxide or t-butyl hydroperoxide.

It is also possible to use combinations of Fe-compounds or Co-compoundswith peroxo salts or salts of bisulfites or hydrosulfites. Thesecombinations are known as redox systems.

The polymerization temperature depends on the initiator used. Usuallythe polymerization temperature is in the range of 5° C. to 95° C. andpreferably from 30° C. to 90°. If pressure is applied the temperaturecan raise up to 120° C., however, polymerization under normal pressureis the usual process.

Alternatively the polymerization can be initiated by photoinitiators andelectromagnetic radiation, in particular actinic radiation.

Photoinitiators suitable for use in the process according to theinvention are in principle any compounds and mixtures that form one ormore free radicals when irradiated with electromagnetic waves. Theseinclude initiator systems consisting of a plurality of initiators andsystems that function independently of one another or synergistically.In addition to coinitiators, for example amines, thiols, borates,enolates, phosphines, carboxylates and imidazoles, it is also possibleto use sensitisers, for example acridines, xanthenes, thiazenes,coumarins, thioxanthones, triazines and dyes. A description of suchcompounds and initiator systems can be found e.g. in Crivello J. V.,Dietliker K. K., (1999): Chemistry & Technology of UV & EB Formulationfor Coatings, Inks & Paints, and in Bradley G. (ed.) Vol. 3:Photo-initiators for Free Radical and Cationic Polymerisation 2ndEdition, John Wiley & Son Ltd. The photoinitiator suitable for theprocess according to the invention in step b) may be either an initiatorhaving an unsaturated group or an initiator not having such a group

Such compounds and derivatives are derived, for example, from thefollowing classes of compounds: benzoins, benzil ketals, acetophenones,hydroxyalkylphenones, aminoalkylphenones, acylphosphine oxides,acylphosphine sulfides, acyloxyiminoketones, alkylamino-substitutedketones, such as Michler's ketone, peroxy compounds, dinitrilecompounds, halogenated acetophenones, phenylglyoxylates, dimericphenylglyoxalates, benzophenones, oximes and oxime esters,thioxanthones, coumarins, ferrocenes, titanocenes, onium salts,sulfonium salts, iodonium salts, diazonium salts, borates, triazines,bisimidazoles, polysilanes and dyes. It is also possible to usecombinations of the compounds from the mentioned classes of compoundswith one another and combinations with corresponding coinitiator systemsand/or sensitisers.

Surprisingly it has been found that after polymerization has beencompleted, the volatile components, water mainly, can be removed withoutagglomeration of the particles. The polymer particles can thereforereadily be re-dispersed, if desired.

Vaporization of the volatile components can be carried out usingstandard methods, such as for example spray drying.

Consequently another aspect of the invention is a polymer powderobtainable by vaporizing the volatile components of the concentratedaqueous polymer dispersion as described above.

The polymer powder containing highly concentrated light stabilizers canbe used for example in the formulation of powder coatings or for plasticapplications in mold, blow mold or extrusion processes.

The instant invention pertains further to a composition stabilizedagainst thermal, oxidative or light-induced degradation which comprises,

-   -   (a) an organic material susceptible to thermal, oxidative or        light induced degradation, and    -   (b) a concentrated aqueous polymer dispersion as described        above.

For instance the organic material is a recording material.

For example the recording material is a photographic material or an inkjet material.

In another embodiment of the invention the recording material is aprinted material containing the concentrated aqueous polymer dispersionin an overprint varnish.

Materials to be stabilized with the instant novel polymer dispersionsare for example recording materials. By such materials are meant, forexample, those described in Research Disclosure 1990, 31429 (pages474-480) for photographic reproduction and other reprographictechniques.

The recording materials comprise, for example, those forpressure-sensitive copying systems, microcapsule photocopier systems,heat-sensitive copier systems, photographic material and ink-jetprinting.

The recording materials feature an unexpectedly high quality, especiallyin terms of their light stability.

The recording materials have a structure which is known per se and whichcorresponds to the utility. They consist of a base, for example paper orplastic film, on which one or more coatings are applied. Depending onthe type of material, these coats contain the suitable componentsrequired, in the case of photographic material for example silver halideemulsions, colour couplers, dyes and the like. The material intendedespecially for ink-jet printing has a customary base on which there isan absorption layer suitable for ink. Uncoated paper can likewise beemployed for ink-jet printing; in this case, the paper functionssimultaneously as a base and has the absorbent for the ink. Suitablematerial for ink-jet printing is described, inter alia, in U.S. Pat. No.5,073,448, the disclosure content of which is regarded as part of thepresent description.

The recording material can also be transparent, for example in the caseof projection films.

The polymer dispersions can be incorporated into the material even inthe course of manufacture; in papermaking, for example, by addition tothe pulp. Another method of use is the spraying of the material or theaddition thereof to the coating.

Coatings for transparent recording materials for projection must notcontain any light-scattering particles such as pigments or fillers.

The colour-binding coatings can contain further additives, for exampleantioxidants, light stabilizers, viscosity improvers, brighteners,biocides and/or antistats.

The coating is usually prepared as follows:

The water-soluble components, for example the binder, are dissolved inwater and mixed. The solid components, for example fillers and otheradditives as already described, are dispersed in this aqueous medium.Dispersion is advantageously brought about with the aid of equipmentsuch as ultrasonic devices, turbine agitators, homogenizers, colloidmills, bead mills, sand mills, high-speed stirrers and the like. Aparticular advantage of the instant polymer dispersions is their ease ofincorporation into the coating.

As mentioned, the recording materials cover a broad field of use. Thepolymer dispersions can be employed, for example, in pressure-sensitivecopier systems. They can be added to the paper to protect themicroencapsulated dye precursors against light, or to the binder of thedeveloper layer for protecting the dyes formed therein.

Photocopier systems with light-sensitive microcapsules which aredeveloped by pressure are described, inter alia, in U.S. Pat. Nos.4,416,966; 4,483,912; 4,352,200; 4,535,050; 4,5365,463; 4,551,407;4,562,137 and 4,608,330; and also in EP-A-139,479; EP-A-162,664;EP-A-164,931; EP-A-237,024; EP-A-237,025 and EP-A-260,129. In all thesesystems the polymer dispersions can be added to the colour-acceptinglayer. Alternatively, they can be added to the donor layer forprotecting the colour formers against light.

The polymer dispersions can also be employed in recording materialswhich are based on the principle of photopolymerization, photosofteningor the rupture of microcapsules, or when heat-sensitive orphotosensitive diazonium salts, leuco dyes with oxidizing agent orcolour lactones with Lewis acids are used.

Heat-sensitive recording material exploits the colour-imparting reactionbetween a colourless or weakly coloured base dye and an organic orinorganic colour developer, the recorded image being produced byheat-induced contact of the two materials. This type of heat-sensitiverecording material is very widespread, not only as the recording mediumfor faxes, computers, etc., but also in many other fields, for examplein label printing.

The heat-sensitive recording material is composed of a base, aheat-sensitive colour-forming recording layer on this base, and,optionally, a protective layer on the heat-sensitive, colour-formingrecording layer. The heat-sensitive, colour-forming recording layercontains as its principal constituent a colour-imparting compound and acolour-developing compound, and also a polymer dispersions according tothe instant invention. If the said protective layer is present, thepolymer dispersions can also be incorporated into the protective layer.

Heat-sensitive recording materials are described, for example, in JP-A8-267 915.

Further fields of use are recording materials for dye diffusion transferprinting, thermal wax transfer printing and dot matrix printing, and foruse with electrostatic, electrographic, electrophoretic, magnetographicand laser-electrophotographic printers, recorders or plotters. Of thematerials mentioned, preference is given to recording materials for dyediffusion transfer printing, as are described, for example, inEP-A-507,734.

The polymer dispersions can also be employed in inks, preferably forink-jet printing, for example those as described in U.S. Pat. No.5,098,477, the disclosure content of which is regarded as part of thepresent description. The ink, especially for ink-jet printing, containspreferably water. Inks contain the polymer dispersions usually in aconcentration of from 0.01 to 20% by weight, in particular from 0.5 to10% by weight.

Examples of colour photographic materials are colour negative films,colour reversal films, colour positive films, colour photographic paper,colour reversal photographic paper, colour-sensitive materials for thedye diffusion transfer process or the silver dye bleach process.

Examples of suitable bases for the production of colour photographicmaterials are films and sheets of semisynthetic and synthetic polymers,such as cellulose nitrate, cellulose acetate, cellulose butyrate,polystyrene, polyvinyl chloride, polyethylene terephthalate andpolycarbonate, and paper laminated with a barytes layer or an α-olefinpolymer layer (e.g. polyethylene). These bases can have been colouredwith dyes or pigments, for example titanium dioxide. They can also havebeen coloured black for the purposes of light shielding. The surface ofthe base is generally subjected to a treatment for improving theadhesion of the photographic emulsion layer, for example coronadischarge with subsequent application of a substrate layer.

The recording material preferably comprises the silver halide emulsionlayers starting from the base, in the sequence blue-sensitive,green-sensitive and red-sensitive layer. In the colour photographicmaterial the polymer dispersion is preferably in a layer above thegreen-sensitive layer, particularly preferably in a layer above thesilver halide emulsion layer(s).

The polymer dispersion is preferably present in the photographicmaterial in an amount of from 0.001 to 10 g per m², for example from 0.1to 8 g/m², especially from 0.005 to 6 and, in particular, from 0.01 to 4g/m².

Preference is generally given to a photographic recording materialcomprising the polymer dispersion in a layer above the silver halideemulsion layer(s). Preference is also given to photographic recordingmaterial comprising at least one each of a red-sensitive andgreen-sensitive silver halide emulsion layer and, in between them, aninterlayer, where at least one of the instant polymer dispersions ispresent in the interlayer between the red-sensitive and thegreen-sensitive silver halide emulsion layer. Very particularlypreferred photographic recording material comprises at least one each ofa red-sensitive, a green-sensitive and a blue-sensitive silver halideemulsion layer and also at least two interlayers between theaforementioned layers and a protective layer, where at least one of theinstant polymer dispersions is present in at least one layer above thegreen-sensitive silver halide emulsion layer, and the silver halideemulsion layers contain dark-storage stabilizers and/or lightstabilizers.

Essential constituents of the colour-photographic emulsion layers arebinders, silver halide particles and colour couplers.

Of especial interest, for example, is a colour photographic recordingmaterial comprising, on a base, at least one blue-sensitive silverhalide emulsion layer containing at least one yellow coupler, at leastone green-sensitive silver halide emulsion layer containing at least onemagenta coupler, at least one red-sensitive silver halide emulsion layercontaining at least one cyan coupler, and customary top layer(s) andinterlayer(s), at least one of the layers comprising a polymerdispersion according to the instant invention.

The photographic emulsions can be spectrally sensitized using methinedyes or other dyes. Particularly suitable dyes are cyanine dyes andmerocyanine dyes, including complex merocyanine dyes.

An overview of the polymethine dyes which are suitable as spectralsensitizers, their appropriate combinations and supersensitizingcombinations is given in Research Disclosure 17643 (December 1978),Chapter IV.

The differently sensitized emulsion layers are allocated non-diffusingmonomeric or polymeric colour couplers, which may be located in the samelayer or in an adjacent layer. It is common to assign cyan couplers tothe red-sensitive layers, magenta couplers to the green-sensitive layersand yellow couplers to the blue-sensitive layers.

Preferred is a composition wherein the organic material is an adhesive,an aqueous emulsion of a natural or synthetic rubber, a water based inkor a water based coating.

In step (ii) preferably a non-ionic, cationic or anionic surfactant ispresent.

Preferably the amount of component b) is from 0.1 to 40%, in particularfrom 0.1 to 20% and especially from 0.1 to 10% by weight based on theweight of the solid content of component a).

For very thin film applications the amount of component b) may be ashigh as 60% by weight based on the weight of the solid content ofcomponent a).

Adhesives are preferably selected from the group consisting ofpolyurethanes, polyacrylics, epoxys, phenolics, polyimides, poly(vinylbutyral), polycyanoacrylates, polyacrylates, ethylene/acrylic acidcopolymers and their salts (ionomers), silicon polymers,poly(ethylene/vinyl acetate), atatic polypropylene, styrene-dienecopolymers, polyamides, hydroxyl-terminated polybutadiene,polychloroprene, poly(vinyl acetate), carboxylated styrene/butadienecopolymers and poly(vinyl alcohol).

Aqueous emulsions of natural or synthetic rubber, are for examplenatural latex or latices of carboxylated styrene/butadiene copolymers.

The concentrated aqueous polymer dispersions can also be employed ininks, preferably for ink jet printing.

When water-soluble, water miscible or water dispersible coatings aredesired ammonium salts of acid groups are present in the resin backbone.

The coatings can be physically drying systems or crosslinked polymers.For example crosslinked polymers are derived from aldehydes on the onehand and phenols, ureas and melamines on the other hand, such asphenol/formaldehyde resins, urea/formaldehyde resins andmelamine/formaldehyde resins.

Drying and non-drying alkyd resins are also possible.

Unsaturated polyester resins derived from copolyesters of saturated andunsaturated dicarboxylic acids with polyhydric alcohols and vinylcompounds as crosslinking agents, and also halogen-containingmodifications thereof of low flammability can be used.

Preferred are crosslinkable acrylic resins derived from substitutedacrylates, for example epoxy acrylates, urethane acrylates or polyesteracrylates.

Alkyd resins, polyester resins and acrylate resins crosslinked withmelamine resins, urea resins, polyisocyanates or epoxy resins.

Also crosslinked epoxy resins derived from polyepoxides can beformulated, for example from bisglycidyl ethers or from cycloaliphaticdiepoxides.

The alkyd resin lacquers are the conventional stoving lacquers which areused in particular for coating automobiles (automobile finishinglacquers), for example lacquers based on alkyd/melamine resins andalkyd/acrylic/melamine resins (see H. Wagner and H. F. Sarx,“Lackkunstharze” (1977), pages 99-123). Other crosslinking agentsinclude glycouril resins, blocked isocyanates or epoxy resins.

The lacquers are suitable both for metal finish coatings and solid shadefinishes, especially in the case of retouching finishes, as well asvarious coil coating applications. The lacquers stabilized in accordancewith the invention are preferably applied in the conventional manner bytwo methods, either by the single-coat method or by the two-coat method.In the latter method, the pigment-containing base coat is applied firstand then a covering coat of clear lacquer over it.

The coatings may also be applied onto wood substrates to prevent thewood from discoloration.

Aqueous coating materials can be based on water-soluble, water-thinnablepolymers or polymer dispersions. Highly polar organic film formers, suchas polyvinyl alcohols, polyacrylamides, polyethylene glycols, cellulosederivatives, acrylates and polyesters with very high acid value areexamples for water-soluble polymers. Water-thinnable film formersconsist of relatively short-chain polymers with acid or basic groupscapable of salt formation incorporated into the side chains. They areneutralized with suitable bases or acids, which evaporates during filmformation leads to insoluble polymers. Examples thereof are short andmedium oil carboxylic acid alkyd resins, water-thinnable melamineresins, emulsifiable epoxy resins or silicone-based emulsions. Severalpolymer types are used as water-dilutable film formers. Most importantof these are vinyl acetate copolymers with dibutyl maleinates, vinylesters of Versatic acids, acrylic ester acids or terpolymers withethylene and vinyl chloride, vinyl propionates, pure acrylatesconsisting of polyacrylates and polymethacrylates, acrylate copolymerswith styrene and styrene-butadiene copolymers.

The coating material may also be a water-borne radiation-curableformulation of photopolymerisable compounds.

The coating material may also contain further ingredients such aspigments or dyes, fillers, solvents as coalescing agent, accelerators(hardeners) for the binders, waxes or other hydrophobing agents,defoaming agents, levelling agent, wetting agent, rheological additives(thickeners or thixotropic agents), amines or bases for pH adjustment,photoinitiators, biocides, preservatives, fungicides or insecticides.

The coating material may be dried physically or cured chemically at roomtemperature, by stoving or by radiation. Provided the binders arecurable binders, they are normally used together with the hardenerand/or accelerator.

Any coating composition suitable for coating of wood or wood-basedmaterial may be used as aqueous wood coating material. Examples for woodor wood based material are furniture, parquet, window frames, panels,doors, wood core plywood, chipboard and fibreboard. Depending on theirfunction or transparency the wood coating materials can beprimers/impregnating stains, stain blocking primers and exteriortopcoats like woodstains and opaque coatings. Preferable binders arenowadays straight acrylic dispersions, in many cases self-crosslinkingacrylic dispersions or alkyd resin emulsions or hybrid coatings asmixtures thereof. For interior applications such as furniture andparquet water-based lacquers based on mostly self-crosslinking acrylicdispersions, polyurethane dispersions, acrylic polyurethane copolymerdispersions are preferably used. When film properties should fulfillhigh requirements, radiation-curable polymer dispersions or two packsystems consisting of hydroxyl-functional polymer dispersion andwater-dispersible polyisocyanates are preferred.

The aqueous wood coating material can be applied to the wood byconventional techniques, for example by impregnating, spreading,brushing, dipping, deluging, spraying or with roller or curtainmachines. Also impregnating under high pressure or under vacuum ispossible.

In general compositions are preferred wherein component a) is a waterbased coating.

A specific embodiment of the invention is a powder coating compositionstabilized against thermal, oxidative or light-induced degradationcomprising

-   -   a) a solid binder material; and    -   b) a polymer powder containing a light stabilizer as described        above.

By “powder coating compositions” or “powder coatings” is meant thedefinition as described in “Ullmann's Encyclopedia of IndustrialChemistry, 5th, Completely Revised Edition, Vol. A 18”, pages 438 to 444(1991) in Section 3.4. By powder coatings are meant thermoplastic orbakable, crosslinkable polymers, which are applied in powder form topredominantly metallic substrates. The way in which the powder isbrought into contact with the workpiece that is to be coated typifiesthe various application techniques, such as electrostatic powderspraying, electrostatic fluidized-bed sintering, fixed bed sintering,fluidized-bed sintering, rotational sintering or centrifugal sintering.

Preferred organic film-forming binders for the powder coatingcompositions of the invention are stoving systems based, for example, onepoxy resins, polyester-hydroxyalkylamides, polyester-glycolurils,epoxy-polyester resins, polyester-triglycidyl isocyanurates,hydroxy-functional polyester-blocked polyisocyanates, hydroxy-functionalpolyester-uretdiones, acrylate resins with hardener, or mixtures of suchresins.

Polyesters are in general hydroxy- or carboxy-functional and arenormally prepared by condensation of diols and dicarboxylic acids. Byadding polyols and/or polyacids, branched polyesters are obtained whichthen give rise, in the course of baking in the presence of crosslinkers,to network structures which give the coating the desired physicalproperties, such as scratch resistance, impact strength and flexuralstrength. Instead of multifunctional acids it is also possible to useanhydrides or acid chlorides, such as maleic anhydride, itaconicanhydride, phthalic anhydride, terephthalic anhydride,hexahydroterephthalic anhydride, trimellitic anhydride, pyromelliticdianhydride, succinic anhydride, etc. It is also possible to use simpleesters such as dimethyl terephthalate for example, in which case thepolymerization proceeds by transesterification with elimination of thevolatile alcohol. Likewise practicable is a preparation by a combinationof transesterification and condensation. Polyesters can be prepared,furthermore, by polycondensation of hydroxycarboxylic acids such as12-hydroxystearic acid and hydroxypivalic acid, or of the correspondinglactones, such as ε-caprolactone, for example. Examples of dicarboxylicacids and polyacids include terephthalic, isophthalic, adipic, azelaic,sebacic, 1,12-dodecanedioic, pyromellitic, 3,6-dichlorophthalic,succinic, 1,3-cyclohexanedicarboxylic and 1,4-cyclohexanedicarboxylicacids. Examples of diols and polyols include ethylene glycol, propyleneglycol, glycerol, hexanetriol, hexane-2,5-diol, hexane-1,6-diol,pentaerythritol, sorbitol, neopentyl glycol, trimethylolethane,trimethylolpropane, tris-1,4-cyclohexanedimethanol,trimethylpentanediol, 2,2-diethyl-1,3-propanediol,2-methyl-2-butyl-1,3-propanediol, esterdiol 204 (ester of hydroxypivalicacid and neopentyl glycol), hydrogenated bisphenol A, bisphenol A,hydroxypivalic acid, hydroxypivalate esters,2-butyl-2-ethyl-1,3-propanediol, 1,4-butanediol, 2-butene-1,4-diol,2-butyne-1,4-diol or 2-methyl-1,3-propanediol.

Suitable crosslinking agents for carboxy-functional polyesters are epoxycompounds such as Novolac®-epoxy resins, diglycidyl ethers of bisphenolA, hydrogenated bisphenol A and bis-phenol A modified by reaction with,for example, aliphatic dicarboxylic acids. Also suitable are reactiveepoxy compounds, such as triglycidyltriazolidine-3,5-dione, the glycidylesters of polyacids, such as diglycidyl terephthalate and diglycidylhexahydroterephthalate, hydantoin epoxides (U.S. Pat. No. 4,402,983)and, especially, triglycidyl isocyanurate, epoxidized unsaturated fattyacid esters (for example Uranox® from DSM) and Araldit®PT 910 (CibaSpezialitätenchemie AG). Further crosslinking agents forcarboxy-functional polyesters are β-hydroxyalkylamides (U.S. Pat. No.4,076,917), such as the predominantly tetrafunctionalβ-hydroxyalkylamide derivative of adipic acid (Primid® XL552 from Rohm &Haas), for example. Derivatives of melamine, benzoguanimine andglycoluril that have been alkylated with low molecular mass alcoholshave also proved suitable. Examples are tetramethylmethoxyglycoluril(Powderlink® 1174 from American Cyanamid). In addition, bis- andtrisoxazolidines, such as 1,4-bisoxazolidinobenzene, for example, arealso known as crosslinking agents.

More recent are carboxy-functional polyester, which contain chemicallybonded epoxy groups and are thus able to crosslink with themselves(Molhoek et al., 22nd Fatipec Congress, 15-19.5.95, Budapest, Vol. 1,119-132).

In all systems in which an epoxy group or a glycidyl radical reacts witha carboxyl group or with an anhydride in a crosslinking reaction, it ispossible to employ catalysts. Examples are amines or metal compoundssuch as aluminium acetylacetonate or tin octoate, for example.

The polyisocyanate crosslinkers are of particular importance ascrosslinking agents for hydroxy-functional polyesters. In order toprevent premature crosslinking, because of the high reactivity ofisocyanates, and to obtain good levelling of the melted powder, thepolyisocyanates are blocked (internally in the form of a uretdione, oras an adduct with a blocking agent). Blocking agents most commonlyemployed are ε-caprolactam, methyl ethyl ketoxime or butanone oxime.Other suitable blocking agents for isocyanates are described in thepublications by G. B. Guise, G. N. Freeland and G. C. Smith, J. AppliedPolymer Science, 23, 353 (1979) and by M. Bock and H.-U. Maier-Westhuesin “Progress in Product Development for Powder Coating Technology, XIXth Int. Conf. on Organic Coatings, Science and Technol., Athens, 12-16July”, 1993. Examples of blocked and unblocked polyisocyanates include2-methylpentane 1,5-diisocyanate, 2-ethylbutane 1,4-diisocyanate,3(4)-isocyanatomethyl-1-methylcyclohexyl isocyanate,3-isocyanatomethyl-3,5,5-trimethylcyclohexane diisocyanate,tris(isocyanatomethyl)benzene, 4,4′-diisocyanatodicyclohexylmethane,1,4-bis(isocyanatomethyl)cyclohexane, m-tetramethylxylene diisocyanate,p-tetramethylxylene diisocyanate and, in particular, isophoronediisocyanate. For deblocking it is common to add a metallic catalyst,such as tin octoate, dibutyltin oxide or dibutyltin dilaurate, forexample, to the polyisocyanate formulation.

Further suitable crosslinking agents for hydroxy-functional polyestersare anhydrides such as trimellitic anhydride and its reaction productswith diols and diamines. Further examples of such crosslinking agentsare described by T. A. Misev in “Powder Coatings: Chemistry andTechnology”, published by J. Wiley & Sons, Chichester on pages 123 and124.

Polyacrylates, which commonly possess hydroxyl, carboxyl or glycidylfunctionality, are also employed as binders for powder coatings. Theyare prepared by the customary methods, principally from monomers such asstyrene and linear or branched C₁-C₈alkyl esters of acrylic ormethacrylic acid. In addition, other ethylenically unsaturatedcompounds, such as divinylbenzene, acrylamide, methacrylamide,butoxymethylacrylamide, acrylonitrile, butadiene, etc., can be added andcopolymerized. Hydroxyl functionality is ensured by the copolymerizationof hydroxy-functional monomers such as hydroxyethyl acrylate,hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropylmethacrylate, for example. For carboxyl functionality use is made ofethylenically unsaturated acids and anhydrides, such as acrylic,methacrylic, itaconic and crotonic acid, and maleic, itaconic, acrylicor methacrylic anhydrides (U.S. Pat. No. 3,836,604). Glycidylfunctionality is provided, as taught in EP-A-0 256 369 and U.S. Pat. No.3,876,578, by the copolymerization of monomers such as glycidyl acrylateand glycidyl methacrylate. As crosslinking agents for polyacrylates withhydroxyl or carboxyl functionality it is possible in principle to usethe same compounds as already described for the polyesters with hydroxylor carboxyl functionality. Further suitable crosslinking agents are theepoxy compounds of U.S. Pat. No. 0,045,040. Suitable crosslinking agentsfor polyacrylates with glycidyl functionality are dicarboxylic acids,such as sebacic acid and 1,12-dodecanedicarboxylic acid, and anhydrides,such as bistrimellitic anhydride, for example, and the compoundsdescribed in U.S. Pat. No. 3,880,946. DE-A-3 310 545, furthermore,discloses self-crosslinking polyacrylates.

Epoxy resins for powder coatings are usually either Novolac®-epoxyresins or, in particular, those based on aromatic polyols, especiallythose based on bisphenols such as bisphenol A. Also known are modifiedbisphenol epoxy resins, from JP-A-58 187 464 (1982). The epoxy resinsare employed in combination with crosslinkers from the classes of thesolid aliphatic amines, solid aromatic amines, amine adducts, phenolicresins, polyacids and the already described carboxy-functionalpolyesters. Hardeners deserving of very special mention are thedicyandiamides, which are frequently employed together with a catalyst,examples of which are Lewis acids, boron trifluoride-amine complexes,metal complexes, tertiary or quaternary amines, and imidazolinederivatives, such as 2-methylimidazoline.

A further aspect of the invention is a composition stabilized againstthermal, oxidative or light-induced degradation comprising

-   -   a) a thermoplastic polymer and    -   b) a polymer powder as described above.        Thermoplastic polymers are for example polyolefins and all those        polymers summarized under the term engineering plastics, such as        for example polyester, polyamide, polystyrene or polycarbonate.

Still further aspects of the invention are the use of a concentratedaqueous polymer dispersion as described above as stabilizer againstthermal, oxidative or light-induced degradation of organic materials,which are susceptible to thermal, oxidative or light induced degradationand the use of a polymer powder as described above as stabilizer againstthermal, oxidative or light-induced degradation of a powder coating.

The preferences mentioned for the concentrated aqueous polymerdispersion apply also for the stabilized compositions and all othersubjects of the invention.

The compositions stabilized against thermal, oxidative or light-induceddegradation described above may contain further additives, for example,plasticizers, lubricants, emulsifiers, pigments, optical brighteners,flameproofing agents or anti-static agents.

They may also contain light or heat stabilizers which have been added ina conventional product form. When additional UV-absorbers or stericallyhindered amines (HALS) are added they may be selected from the productsmentioned above.

Further additives are those given below.

1. Antioxidants

1.1. Alkylated monophenols, for example2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol,2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol,2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol,2-(α-methylcyclohexyl)-4,6-dimethylphenol,2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol,2,6-di-tert-butyl-4-methoxymethylphenol, nonylphenols which are linearor branched in the side chains, for example 2,6-di-nonyl-4-methylphenol,2,4-dimethyl-6-(1′-methylundec-1′-yl)phenol,2,4-dimethyl-6-(1′-methylheptadec-1′-yl)phenol,2,4-dimethyl-6-(1′-methyltridec-1′-yl)phenol and mixtures thereof.1.2. Alkylthiomethylphenols, for example2,4-dioctylthiomethyl-6-tert-butylphenol,2,4-dioctylthiomethyl-6-methylphenol,2,4-dioctylthiomethyl-6-ethylphenol,2,6-di-dodecylthiomethyl-4-nonylphenol.1.3. Hydroquinones and alkylated hydroquinones, for example2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone,2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol,2,6-di-tertbutylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole,3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenylstearate, bis(3,5-di-tert-butyl-4-hydroxyphenyl)adipate.1.4. Tocopherols, for example α-tocopherol, β-tocopherol, γ-tocopherol,δ-tocopherol and mixtures thereof (vitamin E).1.5. Hydroxylated thiodiphenyl ethers, for example2,2′-thiobis(6-tert-butyl-4-methylphenol), 2,2′-thiobis(4-octylphenol),4,4′-thiobis(6-tert-butyl-3-methylphenol),4,4′-thiobis(6-tert-butyl-2-methylphenol),4,4′-thiobis(3,6-di-sec-amylphenol),4,4′-bis(2,6-dimethyl-4-hydroxyphenyl)-disulfide.1.6. Alkylidenebisphenols, for example2,2′-methylenebis(6-tert-butyl-4-methylphenol),2,2′-methylenebis(6-tert-butyl-4-ethylphenol),2,2′-methylenebis[4-methyl-6-(α-methylcyclohexyl)-phenol],2,2′-methylenebis(4-methyl-6-cyclohexylphenol),2,2′-methylenebis(6-nonyl-4-methylphenol),2,2′-methylenebis(4,6-di-tert-butylphenol),2,2′-ethylidenebis(4,6-di-tert-butylphenol),2,2′-ethylidenebis(6-tert-butyl-4-isobutylphenol),2,2′-methylenebis[6-(α-methylbenzyl)-4-nonylphenol],2,2′-methylenebis[6-(α,α-dimethylbenzyl)-4-nonylphenol],4,4′-methylenebis(2,6-di-tert-butylphenol),4,4′-methylenebis(6-tert-butyl-2-methylphenol),1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol,1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane,ethylene glycol bis[3,3-bis(3′-tert-butyl-4′-hydroxyphenyl)butyrate],bis(3-tert-butyl-4-hydroxy-5-methyl-phenyl)dicyclopentadiene,bis[2-(3′-tert-butyl-2′-hydroxy-5′-methylbenzyl)-6-tert-butyl-4-methylphenyl]terephthalate,1,1-bis-(3,5-dimethyl-2-hydroxyphenyl)butane,2,2-bis(3,5-di-tert-butyl-4-hydroxyphenyl)propane,2,2-bis-(5-tert-butyl-4-hydroxy-2-methylphenyl)-4-n-dodecylmercaptobutane,1,1,5,5-tetra(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane.1.7. O-, N- and S-benzyl compounds, for example3,5,3′,5′-tetra-tert-butyl-4,4′-dihydroxydibenzyl ether,octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate,tridecyl-4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate,tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine,bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate,bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide,isooctyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.1.8. Hydroxybenzylated malonates, for exampledioctadecyl-2,2-bis(3,5-di-tert-butyl-2-hydroxybenzyl)malonate,di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)malonate,didodecylmercaptoethyl-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate,bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.1.9. Aromatic hydroxybenzyl compounds, for example1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene,1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene,2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.1.10. Triazine compounds, for example2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine,2,4,6-tris-(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine,1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate,2,4,6-tris-(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine,1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexahydro-1,3,5-triazine,1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate.1.11. Benzylphosphonates, for exampledimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate,diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate,dioctadecyl3,5-di-tert-butyl-4-hydroxybenzylphosphonate,dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, thecalcium salt of the monoethyl ester of3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.1.12. Acylaminophenols, for example 4-hydroxylauranilide,4-hydroxystearanilide, octylN-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.1.13. Esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid withmono- or polyhydric alcohols, e.g. with methanol, ethanol, n-octanol,i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.1.14. Esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acidwith mono- or polyhydric alcohols, e.g. with methanol, ethanol,n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol,ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethyleneglycol, diethylene glycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane;3,9-bis[2-{3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5,6]-undecane.1.15. Esters of β-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid withmono- or polyhydric alcohols, e.g. with methanol, ethanol, octanol,octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.1.16. Esters of 3,5-di-tert-butyl-4-hydroxyphenyl acetic acid with mono-or polyhydric alcohols, e.g. with methanol, ethanol, octanol,octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.1.17. Amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid e.g.N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamide,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediamide,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazide,N,N′-bis[2-(3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyloxy)ethyl]oxamide(Naugard®XL-1, supplied by Uniroyal).1.18. Ascorbic acid (vitamin C)1.19. Aminic antioxidants, for exampleN,N′-di-isopropyl-p-phenylenediamine,N,N′-di-sec-butyl-p-phenylenediamine,N,N′-bis(1,4-dimethylpentyl)-p-phenylenediamine,N,N′-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine,N,N′-bis(1-methylheptyl)-p-phenylenediamine,N,N′-dicyclohexyl-p-phenylenediamine, N,N′-diphenyl-p-phenylenediamine,N,N′-bis(2-naphthyl)-p-phenylenediamine,N-isopropyl-N′-phenyl-p-phenylenediamine,N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylenediamine,N-(1-methylheptyl)-N′-phenyl-p-phenylenediamine,N-cyclohexyl-N′-phenyl-p-phenylenediamine,4-(p-toluenesulfamoyl)diphenylamine,N,N′-dimethyl-N,N′-disec-butyl-p-phenylenediamine, diphenylamine,N-allyldiphenylamine, 4-isopropoxydiphenylamine,N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine,N-phenyl-2-naphthylamine, octylated diphenylamine, for examplep,p′-di-tert-octyldiphenylamine, 4-n-butylaminophenol,4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol,4-octadecanoylaminophenol, bis(4-methoxyphenyl)amine,2,6-di-tert-butyl-4-dimethylaminomethylphenol,2,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane,N,N,N′,N′-tetramethyl-4,4′-diaminodiphenylmethane,1,2-bis[(2-methylphenyl)amino]ethane, 1,2-bis(phenylamino)propane,(o-tolyl)biguanide, bis[4-(1′,3′-dimethylbutyl)phenyl]amine,tert-octylated N-phenyl-1-naphthylamine, a mixture of mono- anddialkylated tert-butyl/tert-octyldiphenyl-amines, a mixture of mono- anddialkylated nonyldiphenylamines, a mixture of mono- and dialkylateddodecyldiphenylamines, a mixture of mono- and dialkylatedisopropyl/isohexyldiphenylamines, a mixture of mono- and dialkylatedtert-butyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine,phenothiazine, a mixture of mono- and dialkylatedtert-butyl/tert-octylphenothiazines, a mixture of mono- and dialkylatedtert-octylphenothiazines, N-allylphenothiazine,N,N,N′,N′-tetraphenyl-1,4-diaminobut-2-ene,N,N-bis(2,2,6,6-tetramethylpiperid-4-yl-hexamethylenediamine,bis(2,2,6,6-tetramethylpiperid-4-yl)sebacate,2,2,6,6-tetramethylpiperidin-4-one, 2,2,6,6-tetramethylpiperidin-4-ol.2. Metal deactivators, for example N,N′-diphenyloxamide,N-salicylal-N′-salicyloyl hydrazine, N,N′-bis(salicyloyl)hydrazine,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine,3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalyl dihydrazide,oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide,N,N′-diacetyladipoyl dihydrazide, N,N′-bis(salicyloyl)oxalyldihydrazide, N,N′-bis(salicyloyl)thiopropionyl dihydrazide.3. Phosphites and phosphonites, for example triphenyl phosphite,diphenylalkyl phosphites, phenyldialkyl phosphites,tris(nonylphenyl)phosphite, trilauryl phosphite, trioctadecyl phosphite,distearylpentaerythritol diphosphite,tris(2,4-di-tert-butylphenyl)phosphite, diisodecyl pentaerythritoldiphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite,bis(2,4-dicumylphenyl)pentaerythritol diphosphite,bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite,diisodecyloxypentaerythritol diphosphite,bis(2,4-di-tert-butyl-6-methylphenyl)-pentaerythritol diphosphite,bis(2,4,6-tris(tert-butylphenyl)pentaerythritol diphosphite, tristearylsorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl)4,4′-biphenylene diphosphonite,6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenz[d,g]-1,3,2-dioxaphosphocin,bis(2,4-di-tert-butyl-6-methylphenyl)methyl phosphite,bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite,6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenz[d,g]-1,3,2-dioxaphosphocin,2,2′,2″-nitrilo-[triethyltris(3,3′,5,5′-tetra-tert-butyl-1,1′-biphenyl-2,2′-diyl)phosphite],2-ethylhexyl(3,3′,5,5′-tetra-tert-butyl-1,1′-biphenyl-2,2′-diyl)phosphite,5-butyl-5-ethyl-2-(2,4,6-tri-tert-butylphenoxy)-1,3,2-dioxaphosphirane.

The following phosphites are especially preferred:

Tris(2,4-di-tert-butylphenyl)phosphite (Irgafos® 168, Ciba-Geigy),tris(nonylphenyl)phosphite,

4. Hydroxylamines, for example N,N-dibenzylhydroxylamine,N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine,N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine,N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine,N-hexadecyl-N-octadecylhydroxylamine,N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derivedfrom hydrogenated tallow amine.5. Nitrones, for example N-benzyl-alpha-phenylnitrone,N-ethyl-alpha-methylnitrone, N-octyl-alpha-heptylnitrone,N-lauryl-alpha-undecylnitrone, N-tetradecyl-alpha-tridecylnitrone,N-hexadecyl-alpha-pentadecylnitrone,N-octadecyl-alpha-heptadecyinitrone,N-hexadecyl-alpha-heptadecylnitrone,N-ocatadecyl-alpha-pentadecylnitrone,N-heptadecyl-alpha-heptadecylnitrone,N-octadecyl-alpha-hexadecyinitrone, nitrone derived fromN,N-dialkylhydroxylamine derived from hydrogenated tallow amine.6. Thiosynergists, for example dilauryl thiodipropionate or distearylthiodipropionate.7. Peroxide scavengers, for example esters of β-thiodipropionic acid,for example the lauryl, stearyl, myristyl or tridecyl esters,mercaptobenzimidazole or the zinc salt of 2-mercaptobenzimidazole, zincdibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritoltetrakis(β-dodecylmercapto)propionate.8. Polyamide stabilisers, for example copper salts in combination withiodides and/or phosphorus compounds and salts of divalent manganese.9. Basic co-stabilisers, for example melamine, polyvinylpyrrolidone,dicyandiamide, triallyl cyanurate, urea derivatives, hydrazinederivatives, amines, polyamides, polyurethanes, alkali metal salts andalkaline earth metal salts of higher fatty acids, for example calciumstearate, zinc stearate, magnesium behenate, magnesium stearate, sodiumricinoleate and potassium palmitate, antimony pyrocatecholate or zincpyrocatecholate.10. Nucleating agents, for example inorganic substances, such as talcum,metal oxides, such as titanium dioxide or magnesium oxide, phosphates,carbonates or sulfates of, preferably, alkaline earth metals; organiccompounds, such as mono- or polycarboxylic acids and the salts thereof,e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodiumsuccinate or sodium benzoate; polymeric compounds, such as ioniccopolymers (ionomers). Especially preferred are1,3:2,4-bis(3′,4′-dimethylbenzylidene)sorbitol,1,3:2,4-di(paramethyldibenzylidene)sorbitol, and1,3:2,4-di(benzylidene)sorbitol.11. Fillers and reinforcing agents, for example calcium carbonate,silicates, glass fibres, glass bulbs, asbestos, talc, kaolin, mica,barium sulfate, metal oxides and hydroxides, carbon black, graphite,wood flour and flours or fibers of other natural products, syntheticfibers.12. Other additives, for example plasticisers, lubricants, emulsifiers,pigments, rheology additives, catalysts, flow-control agents, opticalbrighteners, flameproofing agents, antistatic agents and blowing agents.13. Benzofuranones and indolinones, for example those disclosed in U.S.Pat. No. 4,325,863; U.S. Pat. No. 4,338,244; U.S. Pat. No. 5,175,312;U.S. Pat. No. 5,216,052; U.S. Pat. No. 5,252,643; DE-A-4316611;DE-A-4316622; DE-A-4316876; EP-A-0589839 or EP-A-0591 102 or3-[4-(2-acetoxyethoxy)phenyl]-5,7-di-tert-butylbenzofuran-2-one,5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)phenyl]-benzofuran-2-one,3,3′-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy]phenyl)benzofuran-2-one],5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one,3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one,3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butylbenzofuran-2-one,3-(3,4-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one,3-(2,3-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one.

Aside form the above mentioned components, coating composition of theinvention may contain further additives as typically used in paints andlacquers: like slip- and leveling agents, wetting agents, pigments,pigment dispersants, defoamers, matting agents, waxes, anti skinningadditives, adhesion promoters, in can stabilizers, coalescents, rheologymodifiers, sag control agents and thixotropic agents.

The following examples illustrate the invention.

General

Particle size distribution is measured by dynamic light scattering (DLS,90° scattering angle, Nicomp Model 380, Particle Sizing System, SantaBarbara, Calif., USA) and to determine the mean intensity diameter(D_(INT)).

The ultrasonic sound treatment is carried out with a SONOPLUS HD 2200(commercial equipment from BANDELIN electronic GmbH & Co. KG, generatorGM 2200 with ultrasonic converter UW 2200, booster horn SH 213 G andtitanium flat tip TT19). Typically a treatment of 3 min at 60 percentpower is applied for 500 ml oil/water emulsion.

Monomers are used as received without further purification.

Water-borne product forms of the following hydrophobic UV-absorbers areprepared

A PREPARATION EXAMPLES Example A1

For the preparation of a stable oil/water emulsion 20 g of compound 101are dissolved in 20 g methyl methacrylate (MMA), 1.6 g stearylmethacrylate (SMA) and 0.06 g butandioldiacrylate (BDDA). The oil phaseis added dropwise to a stirred solution of 1.6 g sodium dodecylsulphatein 56.5 g deionised water. After stirring for 30 min and ultrasonicallyconverting a kinetically stable emulsion is obtained with an averagedroplet size below 250 nm. The emulsion is heated up to 55° C. and theredox initiator (0.06 g ascorbic acid dissolved in 3 g deionised water;0.25 ml H₂O₂ (35%) diluted in 0.5 g deionised water) is subsequentlyadded to the reaction mixture. The reaction mixture is continuouslystirred by a mechanical stirrer and is maintained at 55° C. for threehours, then cooled to room temperature (RT) and filtered via a 20 μmfilter. The resulting particle size D_(INT) is 141 nm. The activecontent of compound 101 is 20 wt %, based on the total weight of theemulsion.

Example A2

For the preparation of a stable oil/water emulsion 24 g of compound 101are dissolved in 16 g methyl methacrylate (MMA), 1.6 g stearylmethacrylate (SMA) and 0.05 g butandioldiacrylate (BDDA). The oil phaseis added dropwise to a stirred solution of 1.6 g sodium dodecylsulphatein 56.5 g deionised water. After stirring for 30 min and ultrasonicallyconverting a kinetically stable emulsion is obtained with an averagedroplet size below 250 nm. The emulsion is heated up to 55° C. and theredox initiator (0.08 g ascorbic acid dissolved in 3 g deionised water;0.32 ml H₂O₂ (35%) diluted in 0.5 g deionised water) is subsequentlyadded to the reaction mixture. The reaction mixture is continuouslystirred by a mechanical stirrer and is maintained at 55° C. for threehours, then cooled to RT and filtered via a 20 μm filter. The resultingparticle size D_(INT) is 182 nm. The active content of compound 101 is24 wt %, based on the total weight of the emulsion.

Example A3

For the preparation of a stable oil/water emulsion 20 g of compound 101are dissolved in 20 g ethyl acrylate (EA), 1.6 g stearyl methacrylate(SMA) and 0.06 g butandioldiacrylate (BDDA). The oil phase is addeddropwise to a stirred solution of 1.6 g sodium dodecylsulphate in 56.5 gdeionised water. After stirring for 30 min and ultrasonically convertinga kinetically stable emulsion is obtained with an average droplet sizebelow 250 nm. The emulsion is heated up to 55° C. and the redoxinitiator (0.06 g ascorbic acid dissolved in 3 g deionised water; 0.25ml H₂O₂ (35%) diluted in 0.5 g deionised water) is subsequently added tothe reaction mixture. The reaction mixture is continuously stirred by amechanical stirrer and is maintained at 55° C. for three hours, thencooled to RT and filtered via a 20 μm filter. The resulting particlesize D_(INT) is 156 nm. The active content of compound 101 is 20 wt %,based on the total weight of the emulsion.

Example A4

For the preparation of a stable oil/water emulsion 24 g of compound 101is dissolved in 16 g ethyl acrylate (EA), 1.6 g stearyl methacrylate(SMA) and 0.05 g butandioldiacrylate (BDDA). The oil phase is addeddropwise to a stirred solution of 1.6 g sodium dodecylsulphate in 56.5 gdeionised water. After stirring for 30 min and ultrasonically convertinga kinetically stable emulsion is obtained with an average droplet sizebelow 250 nm. The emulsion is heated up to 55° C. and the redoxinitiator (0.08 g ascorbic acid dissolved in 3 g deionised water; 0.32ml H₂O₂ (35%) diluted in 0.5 g deionised water) is subsequently added tothe reaction mixture. The reaction mixture is continuously stirred by amechanical stirrer and is maintained at 55° C. for three hours, thencooled to RT and filtered via a 20 μm filter. The resulting particlesize D_(INT) is 199 nm. The active content of compound 101 is 24 wt %,based on the total weight of the emulsion.

Example A5

For the preparation of a stable oil/water emulsion 40 g of compound 101are dissolved in 40 g methyl methacrylate (MMA), 4.8 g stearylmethacrylate (SMA) and 0.12 g butandioldiacrylate (BDDA). The oil phaseis added dropwise to a stirred solution of 10.3 g Disponil® FES 32 IS(31 wt % active, Cognis Deutschland GmbH&Co.KG) in 115 g deionisedwater. After stirring for 30 min and ultrasonically converting akinetically stable emulsion is obtained with an average droplet sizebelow 250 nm. The emulsion is heated up to 55° C. and the redoxinitiator (0.2 g ascorbic acid dissolved in 3 g deionised water; 0.81 mlH₂O₂ (35%) diluted in 2.0 g deionised water) is subsequently added tothe reaction mixture. The reaction mixture is continuously stirred by amechanical stirrer and is maintained at 55° C. for three hours, thencooled to RT and filtered via a 20 μm filter. The resulting particlesize D_(INT) is 170 nm. The active content of compound 101 is 20 wt %,based on the total weight of the emulsion.

Example A6

The following samples were prepared with a monomer mixture (Mix I),containing 11% hydroxyethyl methacrylate, 15% vinyl toluol, 15%cyclohexyl methacrylate, 28% methyl methacrylate and 31% iso-butylmethacrylate. For the preparation of a stable oil/water emulsion 40 g ofcompound 102 are dissolved in 40 g of Mix I, 3.2 g stearyl methacrylate(SMA) and 0.12 g butandioldiacrylate (BDDA). The oil phase is addeddropwise to a stirred solution of 10.3 g Disponil® FES 32 IS (31 wt %active, Cognis Deutschland GmbH&Co.KG) in 110 g deionised water. Afterstirring for 30 min and ultrasonically converting a kinetically stableemulsion is obtained with an average droplet size below 250 nm. Theemulsion is heated up to 55° C. and the redox initiator (0.2 g ascorbicacid dissolved in 5 g deionised water; 0.81 ml H₂O₂ (35%) diluted in 5.0g deionised water) is subsequently added to the reaction mixture. Thereaction mixture is continuously stirred by a mechanical stirrer and ismaintained at 55° C. for three hours, then cooled to RT and filtered viaa 20 μm filter. The resulting particle size D_(INT) is 198 nm. The finalactive content of compound 102 is 20 wt %, based on the total weight ofthe emulsion.

Example A7

For the preparation of a stable oil/water emulsion 40 g compound 102 aredissolved in 40 g of Mix I and 3.2 g stearyl methacrylate (SMA). The oilphase is added dropwise to a stirred solution of 10.3 g Disponi®I FES 32IS (31 wt % active, Cognis Deutschland GmbH&Co.KG) in 110 g deionisedwater. After stirring for 30 min and ultrasonically converting akinetically stable emulsion is obtained with an average droplet sizebelow 250 nm. The emulsion is heated up to 55° C. and the redoxinitiator (0.2 g ascorbic acid dissolved in 5 g deionised water; 0.81 mlH₂O₂ (35%) diluted in 5.0 g deionised water) is subsequently added tothe reaction mixture. The reaction mixture is continuously stirred by amechanical stirrer and is maintained at 55° C. for three hours, thencooled to RT and filtered via a 20 μm filter. The resulting particlesize D_(INT) is 198 nm. The final active content of compound 102 is 20wt %, based on the total weight of the emulsion.

Example A8

For the preparation of a stable oil/water emulsion 40 g of compound 102are dissolved in 40 g of Mix I, 3.2 g stearyl methacrylate (SMA) and0.06 g dodecyl mercaptane (DDM). The oil phase is added dropwise to astirred solution of 10.3 g Disponil® FES 32 IS (31 wt % active, CognisDeutschland GmbH&Co.KG) in 110 g deionised water. After stirring for 30min and ultrasonically converting a kinetically stable emulsion isobtained with an average droplet size below 250 nm. The emulsion isheated up to 55° C. and the redox initiator (0.2 g ascorbic aciddissolved in 5 g deionised water; 0.81 ml H₂O₂ (35%) diluted in 5.0 gdeionised water) is subsequently added to the reaction mixture. Thereaction mixture is continuously stirred by a mechanical stirrer and ismaintained at 55° C. for three hours, then cooled to RT and filtered viaa 20 μm filter. The resulting particle size D_(INT) is 198 nm. The finalactive content of compound 102 is 20 wt %, based on the total weight ofthe emulsion.

B COATING APPLICATION EXAMPLES Example B1 Testing of Light Stabilizersin a Clear, Waterborne Penetrating Wood Coating

The test formulation is a commercial waterborne wood coating, whichimparts water repellent properties to the coated wood by hydrophobiccomponents (Woodcare QS with propiconazole from Böhme, Switzerland, ˜12%solid content). The different UV-absorber products are added to theformulation by stirring for 2 h. The fully formulated paints areevaluated for storage stability at room temperature in closed bottles byrating the homogeneity of the formulation after different time intervals(see Table 1). In addition, the non-aged paints are applied on fir woodpanels (one coat with a brush) and tested in accelerated weatheringequipment (QUV tester from Q Panel Company: UV-A 340 nm fluorescentlamps; test cycle: 5 h light 58° C., 1 h dark water spray 22° C.).

TABLE 1 Storage tests and weathering results colour change of coated firwood panels after QUV accelerated weathering; ΔE versus % LS storagestability unexposed sample (product form on total after after afterafter after after No. formulation) 48 h 16 weeks 200 h 400 h 800 h 1000h C1 no LS slight slight 18.5 — — — separation separation e.t.h.* C2 2%LIGNOSTAB 1198 strong strong 5.6 8.2 — — 2% Tinuvin 1130 separationseparation e.t.h.* 1 2% LIGNOSTAB 1198 slight strong 1.4 4.7 7.8 — 5%product of example separation separation A5 (20% active UVA) e.t.h.* 22% LIGNOSTAB 1198 slight strong 2.5 1.6 6.2 6.9 10% product ofseparation separation example A5 (20% e.t.h.* active UVA) *e.t.h.: easyto homogenize; these formulations could be easily re-homogenized bysimple shaking or stirring. C1 and C2 are comparative Weatheringperformance is rated according to colour change ΔE* (Din 6174) measuredwith a spectrophotometer versus the corresponding initial unexposedsample. ΔE* measurement is stopped, when wood graying starts due tolignin degradation.

LIGNOSTAB® 1198 is a commercial sterically hindered amine from CibaSpecialty Chemicals, which is used to prevent lignin degradation inconjunction with UV absorbers.

Tinuvin® 1130 is a commercial UV-absorber from Ciba Specialty Chemicals.

Example B2 Testing of Light Stabilizers in a Clear, Waterborne FilmForming Wood Coating

As test formulation a clear waterborne wood coating based on an acrylicdispersion with the following composition is used (solid contentapproximately 43% by weight):

Neocryl ® XK 90 (from NeoResins) 91.2 parts  Water 4.7 partsEthyldiglykol 3.4 parts Borchigel ® L75 N (from Borchers)/Water (1/1)0.4 parts Dehydran ® 1293 (from Cognis) 0.3 parts Total: 100.0 parts  

The additives given in Table 2 are added to the formulation understirring for 2 h. The formulations are applied by brush to fir woodpanels. Totally three coats are applied with a drying time of one daybetween each coat (approximately 100 g/m² per coat). The fullyformulated paints are evaluated for storage stability at roomtemperature in closed bottles by rating the homogeneity of theformulation after different time intervals The coated wood panels aretested in accelerated weathering equipment (QUV tester from Q PanelCompany: UV-A 340 nm fluorescent lamps; test cycle: 5 h light 58° C., 1h dark water spray 22° C.). Weathering performance is rated by woodcolor change compared to the initial color (before exposure) and bystart of crack formation with the mean of a microscope.

TABLE 2 Storage tests and accelerated weathering results in a clear,film forming acrylic wood coating colour change of coated fir storagewood panels after QUV % LS (product stability accelerated weathering; ΔEfirst form on after versus unexposed sample cracking No solid content) 6month After 400 h After 800 h after C1 no LS ok 27.3 27.1   2000 h C2 2% Tin 1130 ok 19.0 23.0   2000 h 1 10% product of separation 14.918.4 >2800 h example A1 e.t.h.* (20% UVA) 2 10% product of separation14.3 17.2   1600 h example A2 e.t.h.* (24% UVA) 3 10% product ofseparation 15.2 19.0 >2800 h example A3 e.t.h.* (20% UVA) 4 10% productof separation 14.8 19.7 >2800 h example A4 e.t.h.* (24% UVA) *e.t.h.:easy to homogenize - these formulations can be easily re-homogenized bysimple shaking or stirring. C1 and C2 are comparative.

The results in table 2 demonstrate that the product forms according tothe invention show good compatibility and formulation stability combinedwith in most cases significantly improved weathering performance(prolonged durability).

Example B3 Testing of Light Stabilizers in a Waterborne, SlightlyPigmented Penetrating Wood Coating

As coating system a commercially available product from Behr (USA)(Deckplus wood-toned waterproofing wood finish, natural clear) is used.The different UV-absorber products are added to the formulation bystirring for 2 h. The formulations are applied on fir wood panels (onecoat) and tested in accelerated weathering equipment (QUV tester from QPanel Company: UV-A 340 nm fluorescent lamps; test cycle: 5 h light 58°C., 1 h dark water spray 22° C.). Weathering performance is ratedvisually by extent of wood graying due to lignin degradation. LIGNOSTAB1198 is additionally used to improve wood stabilization. The testedproducts did not show any negative influence on storage stability of theformulation.

TABLE 3 Wood graying of Deckplus wood-toned waterproofing wood finishfrom Behr (solid content around 20%) upon accelerated weatheringexposure Rating of % LS wood greying (product form on total after afterNo formulation) 800 h 1200 h C1 no LS strong strong C2 1% LIGNOSTAB 1198slight slight 1% Tin 1130 C3 1% LIGNOSTAB 1198 slight slight 2% Tin 1130C4 1% LIGNOSTAB 1198 slight slight 3% Tin 1130 C5 1% LIGNOSTAB 1198 okvery slight 5% Tin 1130 1 1% LIGNOSTAB 1198 ok very slight 2.5% productof example A5 (20% active UVA)

The product form according to the invention shows improved durability(later start of wood graying) even at much lower treating level (weight%) of the active component in the formulation.

Example B4 Testing of Light Stabilizers in Waterborne 1p and 2pAcrylic/Isocyanate Industrial Coatings

The light stabilizer product forms of examples A6, A7 and A8 are testedin comparison to Tinuvin 1130 in a water borne 1-pack acrylic/blockedpolyisocyanate and two different water borne 2-packacrylic/polyisocyanate coating formulations.

Light stabilizers (1% Tin 292 and 2% active UVA, both based on the totalbinder solid content of the paint system) were added to the fullyformulated paints and tested for homogeneous incorporation, shelfstability at room temperature and at 40° C., pot-life (in the case of 2pformulations) and durability (UVCON and CAM 180 exposure).

In case of the 2p formulations, shelf stability is tested in thecorresponding formulations without the hardener component. Comparison isalways made to the formulation without light stabilizer.

Test Series B4.1: Formulations of Light Stabilizers in Waterborne 1pFormulation (Joncryl-Binder)

TABLE 4.1 3 4 5 1 2 Product of Product of Product of No LS Tin 1130example A6 example A7 example A8 Joncryl 8300¹⁾ 31.2 31.2 31.2 31.2 31.2AMP 90 0.3 0.3 0.3 0.3 0.3 Byk 022²⁾ 0.3 0.3 0.3 0.3 0.3 Surfynol 104S³⁾ 0.3 0.3 0.3 0.3 0.3 DI water 5.3 5.3 5.3 5.3 5.3 Joncryl 8300 47.847.8 47.8 47.8 47.8 Dowanol TPNB 3.5 3.5 3.5 3.5 3.5 Rhodocoat WT 1000⁴⁾11.2 11.2 11.2 11.2 11.2 Byk 022 0.1 0.1 0.1 0.1 0.1 Tinuvin 292⁵⁾ 0.40.4 0.4 0.4 0.4 Tinuvin 1130 — 0.8 — — — Product of example A6 — — 4.2 —— Product of example A7 — — — 4.2 — Product of example A8 — — — — 4.2Total 100.4 101.2 104.6 104.6 104.6 ¹⁾Acrylic dispersion, JohnsonPolymers ²⁾Defoamer, Byk ³⁾Wetting agent, Air Products ⁴⁾Hardener,Rhodia ⁵⁾HALS, Ciba Specialty ChemicalsTest Series B4.2: Formulations of Light Stabilizers in Waterborne 2pFormulation (Macrynal-Binder)

TABLE 4.2 3 4 5 1 2 Product of Product of Product of No LS Tin 1130example A6 example A7 example A8 Macrynal VSM 6299w¹⁾ 87.6 87.6 87.687.6 87.6 Surfynol 104/BG²⁾ 1.8 1.8 1.8 1.8 1.8 Borchigel LW 44³⁾ 0.30.3 0.3 0.3 0.3 (50% in deionised water) Bayowet FT 248⁴⁾ 0.3 0.3 0.30.3 0.3 Borchigol LAC 80⁵⁾ 1.5 1.5 1.5 1.5 1.5 (10% in butoxyl)Deionized water 8.5 8.5 8.5 8.5 8.5 Tinuvin 292⁶⁾ 0.6 0.6 0.6 0.6 0.6Tinuvin 1130 — 1.2 — — — Product of example A6 — — 6.0 — — Product ofexample A7 — — — 6.0 — Product of example A8 — — — — 6.0 Total base100.6 101.8 106.6 106.6 106.6 Rhodocoat WT 2104⁷⁾ 8.0 8.0 8.0 8.0 8.0Tolonate HDT-LV2⁸⁾ 18.7 18.7 18.7 18.7 18.7 Butoxyl 6.6 6.6 6.6 6.6 6.6Total hardener 33.3 33.3 33.3 33.3 33.3 Total base + hardener 133.9135.1 139.9 139.9 139.9 ¹⁾Acrylic dispersion, Solutia ²⁾Wetting agent,Air Products ³⁾Thickener, Borchers ⁴⁾Wetting agent, Borchers ⁵⁾Slippingagent, Borchers ⁶⁾HALS, Ciba Specialty Chemicals ⁷⁾Hardener, Rhodia⁸⁾Hardener, RhodiaTest Series 4.3: Formulations of Light Stabilizers in Waterborne 2pFormulation (Setalux-Binder)

TABLE 4.3 3 4 5 1 2 Product of Product of Product of No LS Tin 1130example A6 example A7 example A8 Setalux 6511 AQ-47¹⁾ 60.2 60.2 60.260.2 60.2 Tafigel PUR 60²⁾ 0.5 0.5 0.5 0.5 0.5 Dehydran 1293³⁾ 0.2 0.20.2 0.2 0.2 Surfynol 104 BG⁴⁾ 1.2 1.2 1.2 1.2 1.2 Byk 301⁵⁾ 0.1 0.1 0.10.1 0.1 Byk 348⁶⁾ 0.1 0.1 0.1 0.1 0.1 DI water 27.2 27.2 27.2 27.2 27.2Setalux 6511 AQ-47 4.8 4.8 4.8 4.8 4.8 DI water 5.7 5.7 5.7 5.7 5.7Tinuvin 292⁷⁾ 0.6 0.6 0.6 0.6 0.6 Tinuvin 1130 — 1.2 — — — Product ofexample A6 — — 6.0 — — Product of example A7 — — — 6.0 — Product ofexample A8 — — — — 6.0 Total base 100.6 101.8 106.6 106.6 106.6Rhodocoat WT 2104⁸⁾ 25.0 25.0 25.0 25.0 25.0 Butylacetate 1.7 1.7 1.71.7 1.7 Butylglycolacetate 0.6 0.6 0.6 0.6 0.6 Methoxypropylacetate 3.03.0 3.0 3.0 3.0 Xylene 3.0 3.0 3.0 3.0 3.0 Total hardener 33.3 33.3 33.333.3 33.3 Total base + hardener 133.9 135.1 139.9 139.9 139.9 ¹⁾Acrylicdispersion, Akzo Nobel Resins ²⁾Thickener, Münzig Chemie ³⁾Defoamer,Cognis ⁴⁾Wetting agent, Air Products ⁵⁾Surface tension agent, Byk⁶⁾Wetting agent, Byk ⁷⁾HALS, Ciba Specialty Chemicals ⁸⁾Hardener, Rhodia

In all test series 4.1, 4.2 and 4.3, the product forms of examples A6,A7 and A8 can be easily and uniformly incorporated into the paints bysimple mixing, in the same way as the comparative example with Tin 1130.In contrast, compound 102, which is the UVA used in the product formsCG43-0365, CG43-0366 and CG43-0367 as such can not be uniformlyincorporated in these formulations.

After 4 weeks of storage at room temperature as well as at 40° C. alltest paints including the control without LS showed no signs ofincompatibilities (i.e. no decrease or increase of viscosity greaterthan 20% of the initial value).

Test Series 4.4: Shelf Stability Test of Formulations 4.2, Viscosity ofFormulations after 4 Weeks Storage

TABLE 4.4 viscosities measured at shear rate 1000 s⁻¹ 3 4 5 1 2 Productof Product of Product of No LS Tin 1130 example A6 example A7 example A8Initial viscosity [mPas] 189 212 163 161 161 Viscosity after 4 weeks atRT 179 210 147 145 148 [mPas] Viscosity after 4 weeks at 188 204 148 160142 40° C. [mPas]Test Series 4.5: Shelf Stability Test of Formulations 4.3, Viscosity ofFormulations after 4 Weeks Storage

TABLE 4.5 viscosities measured at shear rate 1000 s⁻¹ 3 4 5 Product ofProduct of Product of 1 2 example example example No LS Tin 1130 A6 A6A6 Initial viscosity [mPas] 9.5 10.6 9.4 9.5 9.3 Viscosity after 4 weeksat RT 9.5 10.4 9.2 9.1 9.2 [mPas] Viscosity after 4 weeks at 9.4 10.29.3 9.1 9.1 40° C. [mPas]

The paint formulations (without hardener) show no significant viscosityincrease on storage (see table 4.4 and 4.5). This demonstrates that thenew product forms do not impair the shelf stability of such 2p paintformulations.

Test Series 4.6: Appearance of the Paint Film According to Formulations4.3.

The general features of the appearance of the cured clear coat in termsof “Distinction Of Image, short and long wavelength” are not altered inthe presence of the UVA product forms according to examples A6, A8 andA8.

TABLE 4.6 DFT~40-45 μm 3 4 5 1 Product of Product of Product of No 2example example example LS Tin 1130 A6 A7 A8 DOI 93.6 93.4 93.5 93.993.5 short 9.2 9.6 8.0 8.6 7.4 wavelength value long 4.3 4.9 4.3 4.6 4.2wavelength valueTest Series 4.7: UVCON Durability Test of Formulation Series 4.2

TABLE 4.7a DFT~40-45 μm, variation of ΔE* upon UVCON exposure 3 4 5 1Product of Product of Product of No 2 example example example LS Tin1130 A6 A7 A8  500 h UVCON 21.2 8.2 1.7 1.7 1.8 1000 h UVCON 24.5 8.52.0 2.0 1.8 1500 h UVCON 25.0 10.4 3.3 3.3 2.8

TABLE 4.7b DFT~40-45 μm, variation of 60° gloss upon UVCON exposure 3 45 1 Product of Product of Product of No 2 example example example LS Tin1130 A6 A7 A8 Initial 92 92 91 91 91  500 h UVCON 91 92 89 90 90 1000 hUVCON 92 92 91 92 91 1500 h UVCON 81 91 88 91 88

TABLE 4.7c DFT ~40-45 μm, variation of ΔE* upon CAM 180 exposure 1 2 3 45 No Tin Product of Product of Product of LS 1130 example A6 example A7example A8  500 h CAM 180 2.2 0.2 0.4 0.3 0.4 1000 h CAM 180 2.3 0.3 0.30.2 0.2 1500 h CAM 180 2.9 0.5 0.2 0.1 0.2 2000 h CAM 180 3.1 0.7 0.20.2 0.2

TABLE 4.7d DFT ~40-45 μm, variation of 60° gloss upon CAM 180 exposure 12 3 4 5 No Tin Product of Product of Product of LS 1130 example A6example A7 example A8 initial 92 92 90 92 89  500 h CAM 180 92 92 91 9291 1000 h CAM 180 92 92 91 92 90 1500 h CAM 180 90 92 90 91 89 2000 hCAM 180 89 90 89 90 89Test series 4.8: UVCON Durability Test of Formulation Series 4.3.

TABLE 4.8a DFT ~40-45 μm, variation of ΔE* upon UVCON exposure 3 4 5 1 2Product of Product of Product of No Tin example example example LS 1130A6 A7 A8  500 h UVCON 22.0 9.5 3.2 2.8 2.7 1000 h UVCON 27.8 9.9 4.7 5.05.1 1500 h UVCON 31.6 11.3 5.3 5.1 5.0 2000 h UVCON 28.8 16.3 6.6 6.99.0

TABLE 4.8b DFT ~40-45 μm, variation of 60° gloss upon UVCON exposure 1 23 4 5 No Tin Product of Product of Product of LS 1130 example A6 exampleA7 example A8 Initial 95 96 96 96 95  500 h UVCON 85 96 96 96 94 1000 hUVCON 83 92 91 92 91 1500 h UVCON 75 94 94 94 94 2000 h UVCON 72 96 8891 94

TABLE 4.8c DFT ~40-45 μm, variation of ΔE* upon CAM 180 exposure 1 2 3 45 No Tin Product of Product of Product of LS 1130 example A6 example A7example A8  500 h CAM 180 1.7 0.5 0.2 0.3 0.3 1000 h CAM 180 2.4 0.9 0.10.1 0.3 1500 h CAM 180 1.5 0.5 0.2 0.2 0.3 2000 h CAM 180 1.8 1.0 0.30.4 0.6

TABLE 4.8d DFT ~40-45 μm, variation of 60° gloss upon CAM 180 exposure 12 3 4 5 No Tin Product of Product of Product of LS 1130 example A6example A7 example A8 initial 95 96 96 96 94  500 h CAM 180 96 96 96 9692 1000 h CAM 180 95 96 95 96 95 1500 h CAM 180 88 96 95 96 95 2000 hCAM 180 91 96 95 95 94

In comparison to the non-stabilized sample and to Tinuvin® 1130 (Tin1130), the increase of ΔE* upon accelerated exposure is significantlyreduced when using the products of examples A6, A7 and A8. Also glossretention is improved when the paints are stabilized with the productforms according to the instant invention.

C INK JET APPLICATION EXAMPLES Example C1

A gelatin coat of following composition

Component: Amount (per m²) Gelatin 1200 mg Wetting agent 100 mg Productof example 1 300 mg (active)is applied over cyan, magenta and yellow step images made on swellableand nanoporous ink jet photo papers using HP 970Cxi, Lexmark Z65, CanonBJC 8200 and Epson Stylus 890 ink jet printers. After drying of the topcoat, the overcoated prints are irradiated in an Atlas Ci-35 weatheringdevice and checked for light resistance relative to prints protected bya control coating (no UV absorber). The overcoat containing CGL 362clearly prevent photo fade of the prints in comparison to the controlcoating, independent of the ink system or print medium.

D PHOTOGRAPHIC EXAMPLES Example D1 Incorporation into a Gelatin Layerand Action as UV Absorber

A gelatin coat of the following composition (per m²) is applied in thecustomary manner to a polyester base. The polymer dispersion of exampleA1 is incorporated into the gelatin casting solution under gentle mixing(no emulsification step is required)

Component: Amount (per m²) Gelatin 1200 mg Hardener 40 mg Wetting agent100 mg Product of example A1 320 mg (active)

The hardener is potassium salt of 2-hydroxy-4,6-dichloro-1,3,5-triazine.The wetting agent is sodium 4,8-diisobutylnaphthalene-2-sulfonate.

The gelatin coat is dried at 20° C. for 2 days.

A transparent UV absorbing layer is obtained which is suitable for aphotographic recording material, for example as a UV filter coat.

The UV absorption spectrum of the layer is recorded using a Perkin ElmerLambda 15 spectrophotometer. The wavelength of maximum absorption(λ_(max)) as well as the optical density at λ_(max) (OD_(max)) arereported in the table below.

UV absorber λ_(max) OD_(max) CGL 362 355 nm 1.23

Example D2

A polyethylene-coated base material is coated with a gelatin coatcomprising silver bromide and magenta coupler (M-9) of the formula

The gelatin coat includes the following components (per m² of basematerial):

Component AgBr coat Gelatin 5.15 g Hardener 300 mg Wetting agent 85 mgSilver bromide 260 mg Magenta coupler 325 mg Tricresyl phosphate 162 mg

The hardener used is the potassium salt of2,4-dichloro-6-hydroxytriazine; the wetting agent used is the sodiumsalt of diisobutylnaphthalenesulfonic acid.

Step wedges having a density difference of 0.3 log E per step areexposed onto the resulting sample, which is then processed in accordancewith the manufacturer's instructions in the P94 processing process ofAgfa Gevaert for colour negative papers.

After exposure and processing, the density of reflectance in the greenregion is measured at a density of between 0.9 and 1.1 of the wedge.

A gelatin layer comprising the product of example A1 is prepared ontransparent base material as described in Example 1. A control layerwithout UV absorber is prepared in the same manner.

Magenta step wedges are subsequently exposed behind the layer containingthe product of example A1 and the control layer in an Atlas exposureinstrument at 15 kJ/cm² and the reflectance density is measured again.The magenta dye density loss (−ΔD) is greatly reduced by the CGL 362layer in comparison with the control layer.

Example D3

A photographic material having the following layer structure isproduced:

top layer red-sensitive layer second gelatine interlayer green-sensitivelayer first gelatine interlayer blue-sensitive layer polyethylene base

The gelatin layers consist of the following components (per m² of basematerial):

Blue-Sensitive Layer

-   α-(3-benzyl-4-ethoxyhydantoin-1-yl)-α-pivaloyl-2-chloro-5-[α-(2,4-ditamylphenoxy)butanamido]acetanilide    (400 mg)-   α-(1-butylphenylurazol-4-yl)-α-pivaloyl-5-(3-dodecanesulfonyl-2-methylpropanamido)-2-methoxyacetamide    (400 mg)-   Dibutyl phthalate (130 mg)-   Dinonyl phthalate (130 mg)-   Gelatin (1200 mg)-   1,5-Dioxa-3-ethyl-3-[β-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxymethyl]-8,10-diphenyl-9-thia[5.5]spiroundecane    (150 mg)-   bis(1-acryloyl-2,2,6,6-tetramethyl-4-piperidyl)    2,2-bis(3,5-di-t-butyl-4-hydroxybenzyl)malonate (150 mg)-   3,5-di-t-butyl-4-hydroxy(2,4-di-t-amylphenyl)benzoate (150 mg)-   poly(N-t-butylacrylamide) (50 mg)-   blue-sensitive silver chlorobromide emulsion (240 mg)    First Gelatin Interlayer-   gelatin (1000 mg)-   2,5-di-t-octylhydroquinone (100 mg)-   hexyl    5-[2,5-dihydroxy-4-(4-hexyloxycarbonyl-1,1-dimethylbutyl)phenyl]-5-methylhexanoate    (100 mg)-   dibutyl phthalate (200 mg)-   diisodecyl phthalate (200 mg)    Green-Sensitive Layer-   7-chloro-2-{2-[2-(2,4-di-t-amylphenoxy)octanamido]-1-methylethyl}-6-methyl-1H-pyrazolo[1,5-b][1,2,4]triazole    (100 mg)-   6-t-butyl-7-chloro-3-(3-dodecanesulfonylpropyl)-1H-pyrazolo[5,1-o][1,2,4]triazole    (100 mg)-   dibutyl phthalate (100 mg)-   dicresyl phosphate (100 mg)-   trioctyl phosphate (100 mg)-   gelatin (1400 mg)-   3,3,3′,3′-tetramethyl-5,5′,6,6′-tetrapropoxy-1,1′-spirobiindane (100    mg)-   4-(i-tridecyloxyphenyl)thiomorpholine 1,1-dioxide (100 mg)-   4,4′-butylidenebis(3-methyl-6-t-butylphenol) (50 mg)-   2,2′-isobutylidenebis(4,6-dimethylphenol) (10 mg)-   3,5-dichloro-4-(hexadecyloxycarbonyloxy)ethylbenzoate (20 mg)-   3,5-bis[3-(2,4-di-t-amylphenoxy)propylcarbamoyl]sodium    benzenesulfinate (20 mg) green-sensitive silver chlorobromide    emulsion (150 mg)    Second Gelatin Interlayer-   gelatin (1000 mg)-   5-chloro-2-(3,5-di-t-butyl-2-hydroxyphenyl)benzo-1,2,3-triazole (200    mg)-   2-(3-dodecyl-2-hydroxy-5-methylphenyl)benzo-1,2,3-triazole (200 mg)    trinonyl phosphate (300 mg)-   2,5-di-t-octylhydroquinone (50 mg)-   hexyl    5-[2,5-dihydroxy-4-(4-hexyloxycarbonyl-1,1-dimethylbutyl)phenyl]-5-methylhexanoate    (50 mg)    Red-Sensitive Layer-   2-[α-(2,4-di-t-amylphenoxy)butanamido]-4,6-di-chloro-5-ethylphenol    (150 mg)-   2,4-dichloro-3-ethyl-6-hexadecanamidophenol (150 mg)-   4-chloro-2-(1,2,3,4,5-pentafluorobenzamido)-5-[2-(2,4-di-t-amylphenoxy)-3-methylbutanamido]phenol    (100 mg)-   dioctyl phthalate (100 mg)-   dicyclohexyl phthalate (100 mg)-   gelatin (1200 mg)-   5-chloro-2-(3,5-di-t-butyl-2-hydroxyphenyl)benzo-1,2,3-triazole (100    mg)-   2-(3-dodecyl-2-hydroxy-5-methylphenyl)benzo-1,2,3-triazole (100 mg)-   3,5-di-t-butyl-4-hydroxy(2,4-di-t-amylphenyl)benzoate (50 mg)    poly(N-t-butylacrylamide) (300 mg)-   N,N-diethyl-2,4-di-t-amylphenoxyacetamide (100 mg)-   2,5-di-t-octylhydroquinone (50 mg)-   red-sensitive silver chlorobromide emulsion (200 mg)

The topmost layer is prepared with and without UV absorber;

With UV Absorber:

-   2,5-di-t-octylhydroquinone (20 mg)-   hexyl    5-[2,5-dihydroxy-4-(4-hexyloxycarbonyl-1,1-dimethylbutyl)phenyl]-5-methylhexanoate    (20 mg)-   gelatin (400 mg)-   trinonyl phosphate (120 mg)-   UV absorber: product of example A1 (385 mg active)    Without UV Absorber:-   gelatin (800 mg)

The hardener used is 2,4-dichloro-6-hydroxytriazine K salt solution, thewetting agent is the sodium salt of diisobutylnaphthalenesulfonic acid.

Three step wedges with a density difference of 0.3 log E per step areexposed onto each of the samples (with blue, green and red light,respectively). Then the processing process RA-4 (Kodak) for colourpapers is carried out.

After exposure and processing, the reflectance densities in the red forthe cyan step, in the green for the magenta step and in the blue for theyellow step are measured at a density of between 0.9 and 1.1 of thewedges. The wedges are then exposed in an Atlas exposure instrument at atotal of 15 kJ/cm², and the reflectance densities are measured again.

In the case of the magenta wedge as well, the reflectance density beforeand after exposure is measured in the blue for the yellowing.

The presence of the product of example A1 reduces the dye density lossof the cyan, magenta and yellow image dye.

1. A concentrated aqueous polymer dispersion of particles with anaverage particle size of less than 1000 nm said particles comprising a)a polymer carrier prepared by heterophase oil in water radicalpolymerization of at least one ethylenically unsaturated monomerselected from the group consisting of C₁-C₁₈acrylates,C₁-C₁₈methacrylates, acrylic acid, (meth)acrylic acid, styrene,vinyltoluene, hydroxy-functional acrylates, hydroxy-functional(meth)acrylates, acrylates derived from alkoxylated alcohols,(meth)acrylates derived from alkoxylated alcohols, multifunctionalacrylates and multifunctional (meth)acrylates in the presence of b) anon-polar organic light stabilizer, 1 wherein the non-polar organiclight stabilizer has a water solubility of less than 1% by weight atroom temperature and atmospheric pressure, wherein the weight ratio ofnon-polar organic light stabilizer to polymer carrier is greater than100 parts of light stabilizer per 100 parts of carrier and particlecontent of the aqueous polymer dispersion is more than 20% by weightbased on the total weight of the aqueous polymer dispersion.
 2. Aconcentrated aqueous polymer dispersion according to claim 1 comprisingadditionally a non-ionic, cationic or anionic surfactant.
 3. Aconcentrated aqueous polymer dispersion according to claim 1 wherein theweight ratio of non-polar organic light stabilizer to polymer carrier isequal or greater than 120 parts per 100 parts.
 4. A concentrated aqueouspolymer dispersion according to claim 1 wherein the average particlesize is less than 500 nm.
 5. A concentrated aqueous polymer dispersionaccording to claim 1 wherein the non-polar organic light stabilizer isselected from the group consisting of a hydroxyphenyl benzotriazolUV-absorber, a hydroxyphenyl triazine UV-absorber, a hydroxybenzophenoneUV-absorber, an oxalic anilide UV-absorber and a sterically hinderedamine light stabilizer or mixtures thereof.
 6. A concentrated aqueouspolymer dispersion according to claim 5 wherein the hydroxybenzophenoneis of formula I

the 2-hydroxyphenylbenzotriazole is of formula IIa, IIb or IIc

the 2-hydroxyphenyltriazine is of formula III

and the oxanilide is of formula (IV)

in the compounds of the formula (I) v is an integer from 1 to 3 and w is1 or 2 and the substituents Z independently of one another are hydrogen,halogen, hydroxyl or alkoxy having 1 to 12 carbon atoms; in thecompounds of the formula (IIa), R₁ is hydrogen, alkyl having 1 to 24carbon atoms, phenylalkyl having 1 to 4 carbon atoms in the alkylmoiety, cycloalkyl having 5 to 8 carbon atoms or a radical of theformula

R₄ and R₅ independently of one another are alkyl having in each case 1to 5 carbon atoms, or R₄, together with the radical C_(n)H_(2n+1−m),forms a cycloalkyl radical having 5 to 12 carbon atoms, m is 1 or 2, nis an integer from 2 to 20 and M is a radical of the formula —COOR₆ inwhich R₆ is hydrogen, alkyl having 1 to 12 carbon atoms, alkoxyalkylhaving in each case 1 to 20 carbon atoms in the alkyl moiety and in thealkoxy moiety or phenylalkyl having 1 to 4 carbon atoms in the alkylmoiety, R₂ is hydrogen, halogen, alkyl having 1 to 18 carbon atoms, andphenylalkyl having 1 to 4 carbon atoms in the alkyl moiety, and R₃ ishydrogen, chlorine, alkyl or alkoxy having in each case 1 to 4 carbonatoms or —COOR₆ in which R₆ is as defined above, at least one of theradicals R₁ and R₂ being other than hydrogen; in the compounds of theformula (IIb) T is hydrogen or alkyl having 1 to 6 carbon atoms, T₁ ishydrogen, chlorine or alkyl or alkoxy having in each case 1 to 4 carbonatoms, n is 1 or 2 and, if n is 1, T₂ is chlorine or a radical of theformula —OT₃ or

if n is 2, T₂ is a radical of the formula

in which T₃ is hydrogen, alkyl which has 1 to 18 carbon atoms and isunsubstituted or substituted by 1 to 3 hydroxyl groups or by —OCOT₆,alkyl which has 3 to 18 carbon atoms, is interrupted once or severaltimes by —O— or —NT₆- and is unsubstituted or substituted by hydroxyl or—OCOT₆, cycloalkyl which has 5 to 12 carbon atoms and is unsubstitutedor substituted by hydroxyl and/or alkyl having 1 to 4 carbon atoms,alkenyl which has 2 to 18 carbon atoms and is unsubstituted orsubstituted by hydroxyl, phenylalkyl having 1 to 4 carbon atoms in thealkyl moiety, or a radical of the formula —CH₂CH(OH)-T₇

T₄ and T₅ independently of one another are hydrogen, alkyl having 1 to18 carbon atoms, alkyl which has 3 to 18 carbon atoms and is interruptedonce or several times by —O— or —NT₆-, cycloalkyl having 5 to 12 carbonatoms, phenyl, phenyl which is substituted by alkyl having 1 to 4 carbonatoms, alkenyl having 3 to 8 carbon atoms, phenylalkyl having 1 to 4carbon atoms in the alkyl moiety or hydroxyalkyl having 2 to 4 carbonatoms, T₆ is hydrogen, alkyl having 1 to 18 carbon atoms, cycloalkylhaving 5 to 12 carbon atoms, alkenyl having 3 to 8 carbon atoms, phenyl,phenyl which is substituted by alkyl having 1 to 4 carbon atoms,phenylalkyl having 1 to 4 carbon atoms in the alkyl moiety, T₇ ishydrogen, alkyl having 1 to 18 carbon atoms, phenyl which isunsubstituted or substituted by hydroxyl, phenylalkyl having 1 to 4carbon atoms in the alkyl moiety, or —CH₂OT₈, T₈ is alkyl having 1 to 18carbon atoms, alkenyl having 3 to 8 carbon atoms, cycloalkyl having 5 to10 carbon atoms, phenyl, phenyl which is substituted by alkyl having 1to 4 carbon atoms, or phenylalkyl having 1 to 4 carbon atoms in thealkyl moiety, T₉ is alkylene having 2 to 8 carbon atoms, alkenylenehaving 4 to 8 carbon atoms, alkynylene having 4 carbon atoms,cyclohexylene, alkylene which has 2 to 8 carbon atoms and is interruptedonce or several times by —O—, or a radical of the formula—CH₂CH(OH)CH₂OT₁₁OCH₂CH(OH)CH₂— or —CH₂—C(CH₂OH)₂—CH₂—, T₁₀ is alkylenewhich has 2 to 20 carbon atoms and can be interrupted once or severaltimes by —O—, or cyclohexylene, T₁₁ is alkylene having 2 to 8 carbonatoms, alkylene which has 2 to 18 carbon atoms and is interrupted onceor several times by —O—, 1,3-cyclohexylene, 1,4-cyclohexylene,1,3-phenylene or 1,4-phenylene, or T₁₀ and T₆, together with the twonitrogen atoms, are a piperazine ring; in the compounds of formula (IIc)R′₂ is C₁-C₁₂alkyl and k is a number from 1 to 4 in the compounds of theformula (III) u is 1 or 2 and r is an integer from 1 to 3, thesubstituents Y₁ independently of one another are hydrogen, hydroxyl,phenyl or halogen, halogenomethyl, alkyl having 1 to 12 carbon atoms,alkoxy having 1 to 18 carbon atoms, alkoxy having 1 to 18 carbon atomswhich is substituted by a group —COO(C₁-C₁₈alkyl); if u is 1, Y₂ isalkyl having 1 to 18 carbon atoms, phenyl which is unsubstituted orsubstituted by hydroxyl, halogen, alkyl or alkoxy having 1 to 18 carbonatoms; alkyl which has 1 to 12 carbon atoms and is substituted by —COOH,—COOY₈, —CONH₂, —CONHY₉, —CONY₉Y₁₀, —NH₂, —NHY₉, —NY₉Y₁₀, —NHCOY₁₁, —CNand/or —OCOY₁₁; alkyl which has 4 to 20 carbon atoms, is interrupted byone or more oxygen atoms and is unsubstituted or substituted by hydroxylor alkoxy having 1 to 12 carbon atoms, alkenyl having 3 to 6 carbonatoms, glycidyl, cyclohexyl which is unsubstituted or substituted byhydroxyl, alkyl having 1 to 4 carbon atoms and/or —OCOY₁₁, phenylalkylwhich has 1 to 5 carbon atoms in the alkyl moiety and is unsubstitutedor substituted by hydroxyl, chlorine and/or methyl, —COY₁₂ or —SO₂Y₁₃,or, if u is 2, Y₂ is alkylene having 2 to 16 carbon atoms, alkenylenehaving 4 to 12 carbon atoms, xylylene, alkylene which has 3 to 20 carbonatoms, is interrupted by one or more —O— atoms and/or is substituted byhydroxyl, —CH₂CH(OH)CH₂—O—Y₁₅—OCH₂CH(OH)CH₂, —CO—Y₁₆—CO—,—CO—NH—Y₁₇—NH—CO— or —(CH₂)_(m)—CO₂—Y₁₆—OCO—(CH₂)_(m), in which m is 1,2 or 3, Y₈ is alkyl having 1 to 18 carbon atoms, alkenyl having 3 to 18carbon atoms, alkyl which has 3 to 20 carbon atoms, is interrupted byone or more oxygen or sulfur atoms or —NT₆- and/or is substituted byhydroxyl, alkyl which has 1 to 4 carbon atoms and is substituted by—P(O)(OY₁₄)₂, —NY₉Y₁₀ or —OCOY₁₁ and/or hydroxyl, alkenyl having 3 to 18carbon atoms, glycidyl, or phenylalkyl having 1 to 5 carbon atoms in thealkyl moiety, Y₉ and Y₁₀ independently of one another are alkyl having 1to 12 carbon atoms, alkoxyalkyl having 3 to 12 carbon atoms,dialkylaminoalkyl having 4 to 16 carbon atoms or cyclohexyl having 5 to12 carbon atoms, or Y₉ and Y₁₀ together are alkylene, oxaalkylene orazaalkylene having in each case 3 to 9 carbon atoms, Y₁₁ is alkyl having1 to 18 carbon atoms, alkenyl having 2 to 18 carbon atoms or phenyl, Y₁₂is alkyl having 1 to 18 carbon atoms, alkenyl having 2 to 18 carbonatoms, phenyl, alkoxy having 1 to 12 carbon atoms, phenoxy, alkylaminohaving 1 to 12 carbon atoms or phenylamino, Y₁₃ is alkyl having 1 to 18carbon atoms, phenyl or alkylphenyl having 1 to 8 carbon atoms in thealkyl radical, Y₁₄ is alkyl having 1 to 12 carbon atoms or phenyl, Y₁₅is alkylene having 2 to 10 carbon atoms, phenylene or a group-phenylene-M-phenylene- in which M is —O—, —S—, —SO₂—, —CH₂— or—C(CH₃)₂—, Y₁₆ is alkylene, oxaalkylene or thiaalkylene having in eachcase 2 to 10 carbon atoms, phenylene or alkenylene having 2 to 6 carbonatoms, Y₁₇ is alkylene having 2 to 10 carbon atoms, phenylene oralkylphenylene having 1 to 11 carbon atoms in the alkyl moiety, and Y₁₈is alkylene having 2 to 10 carbon atoms or alkylene which has 4 to 20carbon atoms and is 3 interrupted once or several times by oxygen; inthe compounds of the formula (IV) x is an integer from 1 to 3 and thesubstituents L independently of one another are hydrogen, alkyl, alkoxyor alkylthio having in each case 1 to 22 carbon atoms, phenoxy orphenylthio.
 7. A concentrated aqueous polymer dispersion according toclaim 5 wherein the sterically hindered amine is selected from the groupconsisting of bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate,bis(2,2,6,6-tetramethyl-4-piperidyl)succinate,bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate,bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate,bis(1,2,2,6,6-pentamethyl-4-piperidyl)n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensate of1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinicacid, linear or cyclic condensates ofN,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-tert-octylamino-2,6-dichloro-1,3,5-triazine,tris(2,2,6,6-tetramethyl-4-piperidyl)nitrilotriacetate,tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butane-tetracarboxylate,1,1′-(1,2-ethanediyl)-bis(3,3,5,5-tetramethylpiperazinone),4-benzoyl-2,2,6,6-tetramethylpiperidine,4-stearyloxy-2,2,6,6-tetramethylpiperidine,bis(1,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)malonate,3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decan-2,4-dione,bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)succinate, linear or cycliccondensates ofN,N′-bis-(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-morpholino-2,6-dichloro-1,3,5-triazine, the condensate of2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triazineand 1,2-bis(3-aminopropylamino)ethane, the condensate of2-chloro-4,6-di-(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-triazineand 1,2-bis-(3-aminopropylamino)ethane,8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione,3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidin-2,5-dione,3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidyl)pyrrolidine-2,5-dione, amixture of 4-hexadecyloxy- and4-stearyloxy-2,2,6,6-tetramethylpiperidine, a condensation product ofN,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, a condensation product of1,2-bis(3-aminopropylamino)ethane and 2,4,6-trichloro-1,3,5-triazine aswell as 4-butylamino-2,2,6,6-tetramethylpiperidine;N-(2,2,6,6-tetramethyl-4-piperidyl)-n-dodecylsuccinimide,N-(1,2,2,6,6-pentamethyl-4-piperidyl)-n-dodecylsuccinimide,2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro[4,5]decane, areaction product of7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro[4,5]decane und epichlorohydrin,1,1-bis(1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl)-2-(4-methoxyphenyl)ethene,N,N-bis-formyl-N,N-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine,diester of 4-methoxy-methylene-malonic acid with1,2,2,6,6-pentamethyl-4-hydroxypiperidine,poly[methylpropyl-3-oxy-4-(2,2,6,6-tetramethyl-4-piperidyl)]siloxane andreaction product of maleic acid anhydride-α-olefin-copolymer with2,2,6,6-tetramethyl-4-aminopiperidine,1,2,2,6,6-pentamethyl-4-aminopiperidine,2,4-bis[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidine-4-yl)-N-butyl-amino]-6-(2-hydroxyethyl)amino-1,3,5-triazine,1-(2-Hydroxy-2-methylpropoxy)-4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine,5-(2-ethylhexanoyl)oxymethyl-3,3,5-trimethyl-2-morpholinone or acompound

in which n is from 1 to
 15. 8. A process for the preparation of aconcentrated aqueous polymer dispersion with an average particle size ofless than 1000 nm comprising the step of polymerizing at least oneethylenically unsaturated monomer in the presence of a non-polar organiclight stabilizer by heterophase radical polymerization; wherein theweight ratio of non-polar organic light stabilizer to polymer carrierformed from the ethylenically unsaturated monomer is greater than 100parts of light stabilizer per 100 parts of polymer carrier.
 9. A processaccording to claim 8 comprising the steps of a) dissolving, emulsifyingor dispersing a non-polar organic light stabilizer in at least oneethylenically unsaturated monomer; b) preparing a conventional oil inwater emulsion of said light stabilizer dissolved, emulsified ordispersed in at least one ethylenically unsaturated monomer; c)homogenizing the conventional emulsion to a miniemulsion wherein thedroplets of the organic phase have an average diameter below 1000 nm d)polymerizing the miniemulsion by adding a polymerization initiator;wherein the weight ratio of non-polar organic light stabilizer topolymer carrier formed from the ethylenically unsaturated monomer isgreater than 100 parts of light stabilizer per 100 parts of polymercarrier.
 10. A polymer powder obtained by vaporizing the volatilecomponents of the concentrated aqueous polymer dispersion according toclaim
 1. 11. A composition stabilized against thermal, oxidative orlight-induced degradation which comprises, (a) an organic materialsusceptible to thermal, oxidative or light induced degradation, and (b)a concentrated aqueous polymer dispersion according to claim
 1. 12. Acomposition according to claim 11 wherein the amount of component b) isfrom 0.1 to 40% by weight based on the weight of the solid content ofcomponent a).
 13. A composition according to claim 11 wherein theorganic material is a recording material.
 14. A composition according toclaim 13 wherein the recording material is a photographic material or anink jet material.
 15. A composition according to claim 13 wherein therecording material is a printed material containing the concentratedaqueous polymer dispersion in an overprint varnish.
 16. A compositionaccording to claim 11 wherein the organic material (a) is an adhesive,an aqueous emulsion of a natural or synthetic rubber, a water based inkor a water based coating.
 17. A powder coating composition stabilizedagainst thermal, oxidative or light-induced degradation comprising a) asolid binder material; and b) a polymer powder according to claim 10.18. A composition stabilized against thermal, oxidative or light-induceddegradation comprising a) a thermoplastic polymer and b) a polymerpowder according to claim
 10. 19. A method of stabilizing an organicmaterial susceptible to thermal, oxidative or light induced degradation,which comprises incorporating therein a stabilizingly effective amountof a concentrated aqueous polymer dispersion according to claim
 1. 20. Amethod of stabilizing a powder coating against thermal, oxidative orlight-induced degradation, which comprises incorporating therein astabilizingly effective amount of a polymer powder according to claim10.
 21. A concentrated aqueous polymer dispersion according to claim 1wherein the dispersion contains 20% by weight or more of the lightstabilizer b) based on the total weight of the dispersion.